Catalyst Systems and Processes for Poly Alpha-Olefin Having High Vinylidene Content

ABSTRACT

A process for making a poly alpha-olefin (PAO) having a relatively high vinylidene content (or combined vinylidene and tri-substituted vinylene content) and a relatively low vinyl and/or di-substituted vinylene content, as well as a relatively low molecular weight. The process includes: contacting a feed containing a C2-C32 alpha-olefin with a catalyst system comprising activator and a bis-cyclopentadienyl metallocene compound, typically a cyclopentadienyl-benzindenyl group 4 transition metal compound.

PRIORITY CLAIM

This application is claims priority to and the benefit of U.S. Ser. No.62/629,200, filed Feb. 12, 2018, and U.S. Ser. No. 62/732,311, filedSep. 17, 2018.

STATEMENT OF RELATED APPLICATIONS

This application is related to U.S. Ser. No. 15/706,088, filed Sep. 15,2017 (which is published as WO 2018/0094088.

This application is also related to U.S. Ser. No. 15/921,757, filed Mar.15, 2018 (which is published as WO 2018/182982.

FIELD OF THE INVENTION

The present invention relates to poly alpha-olefin (PAO) materials andprocesses for making them. In particular, the present invention relatesto ethylenically unsaturated PAO materials and saturated PAO materialsderived from polymerization of alpha-olefins in the presence of acatalyst system comprising a metallocene-compound specifically designedto yield a high vinylidene content.

BACKGROUND OF THE INVENTION

This section provides background information related to the presentinvention which is not necessarily prior art.

Alpha-olefins, especially those containing about 6 to about 20 carbonatoms, and oligomers thereof have been used as intermediates in themanufacture of detergents, lubricants, or other types of commercialproducts. Longer chain alpha-olefins, such as vinylidene-terminatedpolydecenes are also known and can be useful as building blocksfollowing functionalization or as macromonomers.

Metallocene catalyst systems are known for polymerizing alpha-olefinpolymers and oligomers. For example, U.S. Patent Application PublicationNo. 2005/0159299 discloses polymerization and oligomerization withcatalyst compounds on a specifically treated support and exemplifiespolymerization with a catalyst compound of dimethylsilylbis(2-methyl-4-phenyl-indenyl) zirconium dimethyl on a capped support.Such catalysts however typically produce about 50% vinyl and about 50%vinylidene terminal unsaturations (of the termini that are unsaturated).Another example includes U.S. Pat. No. 8,318,998, which disclosescyclopentadienyl-benzindenyl metallocene compounds useful for productionof alpha-olefin polymers, such as ethylene and or propylene polymers,having high allyl chain end content. The Examples in this publicationshow that the resultant alpha-olefin polymers/oligomers have aproportionally low vinylidene content and a proportionally high vinylcontent. U.S. Patent Application Publication No. 2013/0023633 alsodiscloses metallocene compounds and use thereof in making polyolefinshaving proportionally high vinyl content.

Another example, U.S. Pat. No. 8,748,361, discloses a mixture comprisingunsaturated poly alpha-olefin (uPAO) material made from, e.g.,oligomerization of alpha-olefins in the presence of metallocenecatalysts. It was disclosed in this reference that the uPAOs couldcomprise, among others, vinyls, vinylenes, di-substituted vinylenes, andtri-substituted vinylenes. The vinyls and vinylidenes are terminalolefins, while the di- and tri-substituted vinylene olefins are internalolefins. In this publication, mixtures of the uPAOs produced from thepolymerization step were subsequently hydrogenated by hydrogen using ahydrogenation catalyst. A great majority of the C═C double bonds in themixture were then hydrogenated to form a substantially saturated,stable, aliphatic PAO mixture which, in turn, can be separated bydistillation to obtain a hydrogenated PAO material that is particularlysuitable as the basestock for lubricating oil compositions used invarious applications. To the extent the presence of C═C bonds in the PAOmolecules in a lubricating oil composition is considered generallydetrimental to the performance of the oil, especially to the oxidationstability thereof, it is highly desired that the uPAO has an overallcomposition that would result in saturation of the C═C bonds at a degreeas high as possible in the hydrogenation step.

Recently, however, research and development in various chemical fieldsreveal that the ethylenically unsaturated PAO materials prepared fromoligomerization of linear alpha-olefins can be particularlyadvantageously used as an intermediate for making various specialtychemicals because of the reactivity of the C═C double bond present inmolecular structure of the oligomer molecules. For example, variouschemical functional groups can be bonded to the carbon backbone of theuPAO molecule when a chemical agent reactive with the C═C bond isallowed to contact the uPAO material. The functional group thusintroduced onto the PAO structure can bring about unique properties tothe functionalized and saturated PAO molecules.

It has been found that the reactivity of the C═C bonds in vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes aredifferent with regard to many chemical functionalization agents. For aspecific type of functionalization agent, one or more particular type(s)of olefin(s) may be more desirable than the other(s). In addition, uPAOshaving various molecular weight and molecular weight distribution anddiffering reactivities may be desired for making differing derivativescomprising differing functional groups thereon. It is known thatvinylidenes and tri-substituted vinylenes are more reactive thandi-substituted vinylenes with many common reagents reactive with C═Cdouble bonds.

WO 2017/188602 discloses at paragraph [117]Me₂Si(Me₄Cp)(2-Me-benzindenyl)MCl₂, where the 2 position on thebenzindenyl is methyl.

WO 2012/134720, compound G, discloses 1,3-dimethylbenz[e]indenyl)(Me₅Cp)HfMe₂.

WO 2018/0094088 discloses benzindenyl compounds such as (1,3-dimethylbenz[e]indenyl)(CpMe₅)ZrMe₂ and (1,3-dimethylbenz[e]indenyl)(CpMe₄)ZrMe₂.

Other publications of interest include, but are not necessarily limitedto: U.S. application Ser. No. 12/642,453 filed Dec. 18, 2009; Ser. No.12/533,465 filed Jul. 31, 2009; 61/136,172 filed Aug. 15, 2008;62/477,683 filed Mar. 28, 2017; 62/477,706 filed Mar. 28, 2017; PCTPublication Nos. WO 95/27717; WO 2009/155471; WO 2009/155472; WO2009/155510; WO 2009/155517; WO 2017/155149; WO 2012/133717; WO2018/0094088; WO 2018/182982; U.S. Pat. Nos. 3,367,987; 7,214,745;8,816,027; 8,669,326; 8,940,839; 8,754,170; 8,426,659; 8,841,397;8,501,894; 8,669,330; 8,835,563; 8,841,394; 8,399,724; 8,623,974;8,981,029; 6,403,732; 6,818,585; 7,199,072; US Patent ApplicationPublication Nos. 2018/0094088; 2009/0318644, 2004/0102590; 2017/0233516;Japanese Publication No. JP 2005-336092; JP 2011-037164A; ChinesePublication No. CN 105622807; EP Publication Nos. EP 0 659 756; EP 0 610851; EP 0 283 739; Korean Publication No. KR 1725004; Rulhoff, Sascha,and Kaminsky, “Synthesis and Characterization of Defined BranchedPoly(propylene)s with Different Microstructures by Copolymerization ofPropylene and Linear Ethylene Oligomers (C_(n)=26-28) withMetallocenes/MAO Catalysts,” Macromolecules 16 2006, pp. 1450-1460;Kaneyoshi, Hiromu et al. “Synthesis of Block and Graft Copolymers withLinear Polyethylene Segments by Combination of Degenerative TransferCoordination Polymerization and Atom Transfer Radical Polymerization,”Macromolecules, 38, 2005, pp. 5425-5435; Teuben et al. (J. Mol. Catal.,62, 1990, pp. 277-87); X. Yang et al. (Angew. Chem., Int'l Edn., Engl.,31, 1992, pp. 1375-1377); Small and Brookhart (Macromol., 32, 1999, pp.2120-2130); Weng et al. (Macromol Rapid Comm., 2000, 21, pp. 1103-1107);Macromolecules, 33, 2000, pp. 8541-8548; Moscardi et al. (Organomet.,20, 2001, pp. 1918); Zhu et al. (Macromol., 2002, 35, pp. 10062-10070and Macromol. Rap. Commun., 2003, 24, pp. 311-315); Coates et al.(Macromol., 2005, 38, pp. 6259-6268); Rose et al. (Macromolecules, 2008,41, pp. 559-567); and Janiak and Blank (Macromol. Symp., 236, 2006, pp.14-22).

There remains a need for uPAO materials having a high concentration ofvinylidenes (and/or of vinylidenes and tri-substituted vinylenescombined), as well as for processes for, and catalyst systemsspecifically tailored to, making such uPAO materials.

SUMMARY OF THE INVENTION

This section provides a general summary of the invention, and is not acomprehensive invention of its full scope or all of its features.

One aspect of the invention relates to a process for making a polyalpha-olefin (PAO). The process can include a step of contacting a feedcontaining a C₂-C₃₂ alpha-olefin with a catalyst system comprising ametallocene compound in a polymerization reactor under polymerizationconditions to effect a polymerization reaction to obtain apolymerization reaction mixture comprising vinylidenes, tri-substitutedvinylenes, optionally di-substituted vinylenes, and optionally vinyls.The process can also include a step of obtaining an unsaturated PAOproduct from the polymerization reaction mixture, with the unsaturatedPAO product comprising vinylidenes, tri-substituted vinylenes,optionally di-substituted vinylenes, optionally vinyls, and, optionally,is substantially free of the alpha-olefin feed.

The process can also include a step of obtaining an unsaturated PAOproduct from the polymerization reaction mixture, wherein thepolymerization reaction exhibits a selectivity toward greater than orequal to about 80 mol % vinylidenes, preferably 90 mol % vinylidenes,more preferably 96.5 mol % vinylidenes, based on total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes inthe unsaturated PAO product.

This invention relates to a process for making a poly alpha-olefin, PAO,the process comprising: contacting a feed comprising a C₆-C₃₂alpha-olefin, with a catalyst system comprising a metallocene compoundin a polymerization reactor under polymerization conditions to effect apolymerization reaction to obtain a polymerization reaction mixturecomprising vinylidenes, tri-substituted vinylenes, optionallydi-substituted vinylenes, and optionally vinyls; and obtaining anunsaturated PAO product from the polymerization reaction mixture,wherein the unsaturated PAO product comprises vinylidenes,tri-substituted vinylenes, optionally di-substituted vinylenes,optionally vinyls, wherein the metallocene compound is represented byformula (F-MC):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl orsilylcarbyl group;

R⁴ and R⁵ are each independently a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₃₀ hydrocarbyl or silylcarbyl group whereR⁴ and R⁵, taken together with the carbon atoms in the firstcyclopentadienyl ring to which they are directly connected, collectivelyform one or more substituted or unsubstituted rings annelated to thefirst cyclopentadienyl ring;

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl, silylcarbyl, or germanyl group, and optionally at leastthree of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are not hydrogen;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v, such as 3, 4, or 5;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to v-2, such as 1, 2, or 3.

In some embodiments, the metallocene compound has a structurerepresented by formula (I):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup, preferably wherein a first one of R¹, R², and R³ is a substitutedor unsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; a second one of R¹, R², and R³ is hydrogen; and a third one ofR¹, R², and R³ is hydrogen, a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring;

R¹², R¹³, R¹⁴ and R¹⁵, are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

R¹⁶ is a substituted or unsubstituted linear, branched linear, or cyclicC₁-C₂₀ hydrocarbyl group or silylcarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a transition metal, preferably group 3, 4 or 5, having an integercoordination number of v, such as 3, 4, or 5; and

m is an integer equal to v-2, such as 1, 2, or 3.

Another aspect of the invention relates to a catalyst compound suitableto produce an unsaturated PAO product from C₆-C₃₂ alpha-olefin underpolymerization conditions. In some embodiments, the catalyst compoundcomprises a polymerization selectivity suitable to form an unsaturatedPAO product comprising greater than or equal to about 80 mol %vinylidenes, preferably 90 mol % vinylidenes, more preferably 96.5 mol %vinylidenes, based on total moles of vinyls, vinylidenes, di-substitutedvinylenes, and tri-substituted vinylenes in the unsaturated PAO product;represented by the formula (F-MC2):

in which one of R¹, R², and R³ comprises an alpha Group 14 atom directlyattached to the indenyl ring, and a beta Group 14 atom attached to thealpha atom, and two or more, preferably three, substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroups attached to the beta atom, optionally two of R¹, R², and R³ areeach hydrogen;

R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently a hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R¹², R¹³, R¹⁴ and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₂₀ hydrocarbyl group or silylcarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a transition metal, preferably group 3, 4 or 5 having an integercoordination number of v, preferably 3, 4 or 5; and

m is an integer equal to v-2, such as 1, 2, or 3.

Another aspect of the invention relates to an unsaturated polyalpha-olefin (PAO) product comprising vinylidenes, tri-substitutedvinylenes, optionally di-substituted vinylenes, optionally vinyls. Inparticular embodiments, the unsaturated PAO product comprises greaterthan or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andti-substituted vinylenes contained therein.

Further areas of applicability will become apparent from the descriptionprovided herein. The description and specific examples in this summaryare intended for purposes of illustration only and are not intended tolimit the scope of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a bar graph comparing mole percent vinylidene according to thepolymerization temperature of catalysts according to embodiments of theinvention; and

FIG. 2 is a graph comparing mole percent vinylidene versus M_(n) of1-decene oligomers produced using catalysts and methods according toembodiments of the invention.

DETAILED DESCRIPTION

The term “alkyl” or “alkyl group” interchangeably refers to a saturatedhydrocarbyl group consisting of carbon and hydrogen atoms. An alkylgroup can be linear, branched linear, cyclic, or substituted cyclic.

The term “branched linear” is defined to mean a branched group that isnot dendritic (i.e., branch on branch) or crosslinked, typically abranched linear group is a linear group that has one or more branches,including but not limited to those compounds represented by formula F-Vbelow.

The term “cycloalkyl” or “cycloalkyl group” interchangeably refers to asaturated hydrocarbyl group wherein the carbon atoms form one or morering structures.

The term “alkenyl” or “alkenyl group” interchangeably refers to a linearunsaturated hydrocarbyl group comprising a C═C bond therein.

The term “cycloalkenyl” or “cycloalkenyl group” interchangeably refersto cyclic hydrocarbyl group comprising a C═C bond in the ring.

The term “aryl” or “aryl group” interchangeably refers to a hydrocarbylgroup comprising an aromatic ring structure therein.

Unless otherwise indicated, a substituted group means such a group inwhich at least one atom is replaced by a different atom or a group.Thus, a substituted alkyl group can be an alkyl group in which at leastone hydrogen atom is replaced by a hydrocarbyl group, a halogen, anyother non-hydrogen group, and/or a least one carbon atom and hydrogenatoms bonded thereto is replaced by a different group. Preferably, asubstituted group is a radical in which at least one hydrogen atom hasbeen substituted with a heteroatom or heteroatom containing group,preferably with at least one functional group, such as halogen (Cl, Br,I, F), NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃, and the like or where at least one heteroatom hasbeen inserted within the hydrocarbyl radical, such as halogen (Cl, Br,I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂,PbR*₂, and the like, where R* is, independently, hydrogen or ahydrocarbyl.

The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl”interchangeably refers to a group consisting of hydrogen and carbonatoms only. A hydrocarbyl group can be saturated or unsaturated, linearor branched linear, cyclic or acyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with a heteroatom or heteroatomcontaining group, preferably with at least one functional group, such ashalogen (Cl, Br, I, F), NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least oneheteroatom has been inserted within the hydrocarbyl radical, such ashalogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂,GeR*₂, SnR*₂, PbR*₂, and the like, where R* is, independently, hydrogenor a hydrocarbyl.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this invention, when a radical islisted, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl, and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

Silylcarbyl radicals (also referred to as silylcarbyls, silylcarbylgroups or silylcarbyl substituents) are radicals in which one or morehydrocarbyl hydrogen atoms have been substituted with at least one SiR*3containing group or where at least one —Si(R*)₂— has been insertedwithin the hydrocarbyl radical where R* is independently a hydrocarbylor halocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure. Silylcarbyl radicals canbe bonded via a silicon atom or a carbon atom.

Substituted silylcarbyl radicals are silylcarbyl radicals in which atleast one hydrogen atom has been substituted with at least onefunctional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, GeR*₃, SnR*₃, PbR₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the silylcarbylradical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g., F,Cl, Br, I) or halogen-containing group (e.g., CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at leastone non-carbon atom or group has been inserted within the halocarbylradical such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—,—Sn(R*)₂—, —Pb(R*)₂— and the like, where R* is independently ahydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical. Additionally, two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

The term “Cn” group or compound refers to a group or a compoundcomprising carbon atoms at total number thereof of n. Thus, a “Cm-Cn”group or compound refers to a group or compound comprising carbon atomsat a total number thereof in the range from m to n. Thus, a C₁-C₅₀ alkylgroup refers to an alkyl group comprising carbon atoms at a total numberthereof in the range from 1 to 50.

The term “olefin,” alternatively termed “alkene,” refers to anunsaturated hydrocarbon compound having a hydrocarbon chain containingat least one carbon-to-carbon double bond in the structure thereof,wherein the carbon-to-carbon double bond does not constitute a part ofan aromatic ring. The olefin may be linear, branched linear, or cyclic.For purposes of this specification and the claims appended thereto, whena polymer or copolymer is referred to as comprising an olefin,including, but not limited to ethylene, propylene, and butene, theolefin present in such polymer or copolymer is the polymerized form ofthe olefin. For example, when a copolymer is said to have an “ethylene”content of 35 wt % to 55 wt %, it is understood that the mer unit in thecopolymer is derived from ethylene in the polymerization reaction andsaid derived units are present at 35 wt % to 55 wt %, based upon theweight of the copolymer. A “polymer” has two or more of the same ordifferent mer units. A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. “Different” as usedto refer to mer units indicates that the mer units differ from eachother by at least one atom or are different isomerically. Thus, an“olefin” is intended to embrace all structural isomeric forms ofolefins, unless it is specified to mean a single isomer or the contextclearly indicates otherwise. An oligomer is a polymer having a lowmolecular weight, such as an Mn of 21,000 g/mol or less (preferably10,000 g/mol or less), and/or a low number of mer units, such as 100 merunits or less (preferably 75 mer units or less).

The term “alpha-olefin” refers to an olefin having a terminalcarbon-to-carbon double bond in the structure thereof ((R¹R²)—C═CH₂,where R¹ and R² can be independently hydrogen or any hydrocarbyl group;preferably R¹ is hydrogen and R² is an alkyl group). A “linearalpha-olefin” is an alpha-olefin defined in this paragraph wherein R¹ ishydrogen, and R² is hydrogen or a linear alkyl group. Non-limitingexamples of α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene,1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene,1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene,3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene,vinylcyclohexane, and vinylnorbornane. Non-limiting examples of cyclicolefins and diolefins include cyclobutene, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene,4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene,vinylcyclohexane, norbomadiene, dicyclopentadiene,5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene,1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,1,4-divinylcyclohexane, 1,5-divinylcyclooctane,1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane,1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane.

The term “vinyl” means an olefin having the following formula:

wherein R is a hydrocarbyl group, preferably a saturated hydrocarbylgroup such as an alkyl group.

The term “vinylidene” means an olefin having the following formula:

wherein R¹ and R² are each independently a hydrocarbyl group, preferablya saturated hydrocarbyl group such as alkyl group. Vinylidenes are1,1-di-substituted vinylene groups.

The term “di-substituted vinylene” means:

(i) an olefin having the following formula:

(ii) an olefin having the following formula:

(iii) a mixture of (i) and (ii) at any proportion thereof, wherein R¹and R², the same or different at each occurrence, are each independentlya hydrocarbyl group, preferably saturated hydrocarbyl group such asalkyl group. Di-substituted vinylenes represent only 1,2-di-substitutedvinylene groups and do not include vinylidenes, or 1,1-di-substitutedvinylenes. The term “vinylene,” as used herein, is an alternative termfor “di-substituted vinylene” only and not as a generic class ofmultiple vinylene species.

The term “tri-substituted vinylene” means an olefin having the followingformula:

wherein R¹, R² and R³ are each independently a hydrocarbyl group,preferably a saturated hydrocarbyl group such as alkyl group, oralternatively R¹ and R² can together form a non-aryl ring structure withR³ being a pendant hydrocarbyl group.

As used herein, “poly alpha-olefin(s)” (PAO(s)) are polymers of one ormore alpha-olefin monomers, particularly an oligomer of one or morealpha-olefins. PAOs are polymeric, typically oligomeric, moleculesproduced from the polymerization reactions of alpha-olefin monomermolecules in the presence of a catalyst system, optionally furtherhydrogenated to remove residual carbon-carbon double bonds therein oroptionally further functionalized by reaction with some or all of theresidual carbon-carbon bonds therein. Thus, the PAO can be a dimer, atrimer, a tetramer, or any other oligomer or polymer comprising two ormore structure units derived from one or more alpha-olefin monomer(s).The PAO molecule can be highly regio-regular, such that the bulkmaterial may exhibit an isotacticity, or a syndiotacticity when measuredby ¹³C NMR. The PAO molecule can be highly regio-irregular, such thatthe bulk material can be substantially atactic when measured by ¹³C NMR.A PAO material made by using a metallocene-based catalyst system istypically called a metallocene-PAO (mPAO), and a PAO material made byusing traditional non-metallocene-based catalysts (e.g., Lewis acids,supported chromium oxide, and the like) is typically called aconventional PAO (cPAO).

The term “carbon backbone” refers to the longest straight carbon chainin the molecule of the compound or the group in question. “Branches” or“pendant groups” interchangeably refer to any non-hydrogen groupconnected to the carbon backbone other than those attached to the carbonatoms at the very ends of the carbon backbone. As used herein, the term“length” of a pendant group is defined as the total number of carbonatoms in the longest carbon chain in the pendant group, counting fromthe first carbon atom attached to the carbon backbone and ending withthe final carbon atom therein, without taking into consideration anysubstituents or pendant groups on the chain. In some embodiments, thependant group is free of substituents comprising more than 2 carbonatoms (or more than 1 carbon atom), or is free of any substituent. Apendant group may contain a cyclic group or a portion thereof in thelongest carbon chain, in which case half of the carbon atoms in thecyclic group are counted toward the length of the pendant group. Thus,by way of examples, a linear C₈ pendant group has a length of 8; each ofthe pendant groups PG-1 (cyclohexylmethylene) and PG-2 (phenylmethylene)has a length of 4; and each of the pendant groups PG-3(o-heptyl-phenylmethylene) and PG-4 (p-heptylphenylmethylene) has alength of 11. Where a PAO molecule contains multiple pendant groups, thearithmetic average of the lengths of all such pendant groups iscalculated as the average length of all pendant groups in the PAOmolecule.

In the present invention, any metallocene compound may have one or moreoptical isomers. All metallocene compound identified herein by name orstructure shall include all possible optical isomers thereof andmixtures of any such optical isomers. For example, metallocene compoundMe₂Si(Me₄Cp)(3-PrInd)ZrMe₂ shall include the following two opticalisomers and mixtures thereof, even if only one structure is given whenit is described:

Unless specified otherwise, the term “substantially all” with respect toPAO molecules means at least 90 mol % (such as at least 95 mol %, atleast 98 mol %, at least 99 mol %, or even 100 mol %).

Unless specified otherwise, the term “substantially free of” withrespect to a particular component means the concentration of thatcomponent in the relevant composition is no greater than 10 mol % (suchas no greater than 5 mol %, no greater than 3 mol %, no greater than 1mol %, or about 0%, within the bounds of the relevant measurementframework), based on the total quantity of the relevant composition.

The terms “catalyst” and “catalyst compound” are defined to mean acompound capable of initiating catalysis and/or of facilitating achemical reaction with little or no poisoning/consumption. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor. A “catalyst system”is combination of at least one catalyst compound, at least oneactivator, an optional co-activator, and an optional support material,where the system can polymerize monomers to form polymer.

A scavenger is a compound typically added to facilitateoligomerization/polymerization by scavenging impurities. Some scavengersmay also act as activators and may be referred to as co-activators. Aco-activator, that is not a scavenger, may be used in conjunction withan activator in order to form an active catalyst. In some embodiments, aco-activator can be pre-mixed with the catalyst compound to form analkylated catalyst compound.

As used herein, a “lubricant” refers to a substance that can beintroduced between two or more moving surfaces and lower the level offriction between two adjacent surfaces moving relative to each other. Alubricant “base stock” is a material, typically a fluid at the operatingtemperature of the lubricant, used to formulate a lubricant by admixingit with other components. Non-limiting examples of base stocks suitablein lubricants include API Group I, Group II, Group III, Group IV, GroupV and Group VI base stocks. Fluids derived from Fischer-Tropsch processor Gas-to-Liquid (“GTL”) processes are examples of synthetic base stocksuseful for making modern lubricants. GTL base stocks and processes formaking them can be found, e.g., in PCT Publication No. WO 2005/121280and in U.S. Pat. Nos. 7,344,631; 6,846,778; 7,241,375; and 7,053,254.

All kinematic viscosity values in the present invention are asdetermined according to ASTM D445. Kinematic viscosity at 100° C. isreported herein as KV100, and kinematic viscosity at 40° C. is reportedherein as KV40. Unit of all KV100 and KV40 values herein is cSt, unlessotherwise specified.

All viscosity index (VI) values in the present invention are asdetermined according to ASTM D2270.

All Noack volatility (NV) values in the present invention are asdetermined according to ASTM D5800 unless specified otherwise. Units ofall NV values are wt %, unless otherwise specified.

Unless otherwise indicated, bromine number values in the presentinvention are determined according to ASTM D 1159.

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and consider experimental error and variations that would be expected bya person having ordinary skill in the art.

In the present invention, all percentages of pendant groups, terminalcarbon chains, and side chain groups are by mole, unless specifiedotherwise. Percent by mole is expressed as “mol %,” and percent byweight is expressed as “wt %.”

In the present invention, all molecular weight data are in the unit of gmol⁻¹.

NMR spectroscopy provides key structural information about thesynthesized polymers. Proton NMR (¹H-NMR) analysis is used to determinethe molecular weight of oligomer or polymer materials (includingfunctionalized, hydrogenated, and uPAO materials). However, molecularweights of oligomer or polymer materials measured by ¹H-NMR hereinrepresent a number average molecular weight (Mn). In addition, ¹H-NMRanalysis of the unsaturated PAO product can give a quantitativebreakdown of the olefinic structure types (viz. vinyl, di-substitutedvinylene, tri-substituted vinylene, and vinylidene). In the presentinvention, compositions of mixtures of olefins comprising terminalolefins (vinyls and vinylidenes) and internal olefins (di-substitutedvinylenes and tri-substituted vinylenes) are determined by using ¹H-NMRas described in the experimental section. Carbon-13 NMR (¹³C-NMR) can beused to determine tacticity of the PAOs of the present invention.Carbon-13 NMR can be used to determine the percentages of the triads,denoted (m,m)-triads (i.e., meso, meso), (m,r)—(i.e., meso, racemic) and(r,r)—(i.e., racemic, racemic) triads, respectively. The concentrationsof these triads can define whether the polymer is isotactic, atactic orsyndiotactic. In the present invention, the percentage of the(m,m)-triads in mol % is recorded as the isotacticity of the PAOmaterial. Spectra for a PAO sample are acquired in the following manner.Approximately 100-1000 mg of the PAO sample is dissolved in ˜2-3 ml ofchloroform-d for ¹³C-NMR analysis. The samples are run with a ˜60 sdelay and ˜90° pulse with at least 512 transients. The tacticity can becalculated using the peak around 35 ppm (CH₂ peak next to the branchpoint). Analysis of the spectra can be performed according to the paperby Kim, I.; Zhou, J.-M.; and Chung, H. Journal of Polymer Science: PartA: Polymer Chemistry 2000, 38 1687-1697. The calculation of tacticity ismm*100/(mm+mr+rr) for the molar percentages of (m,m)-triads,mr*100/(mm+mr+rr) for the molar percentages of (m,r)-triads, andrr*100/(mm+mr+rr) for the molar percentages of (r,r)-triads. The(m,m)-triads correspond to ˜35.5-˜34.55 ppm, the (m,r)-triads to˜34.55-˜34.1 ppm, and the (r,r)-triads to ˜34.1-˜33.2 ppm.

The following abbreviations may be used through this specification: Cpis cyclopentadiene or cyclopentadienyl; Me is methyl, Ph is phenyl, Etis ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu isbutyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiarybutyl, nBu is normal butyl, TMS is trimethylsilyl, TIBAL istriisobutylaluminum, TNOAL or TNOA is triisobutyl n-octylaluminum, MAOis methylalumoxane, pMe is para-methyl, Ar* is 2,6-diisopropylaryl, Bzor Bn are interchangeably benzyl, THF is tetrahydrofuran, RT is roomtemperature (i.e., approximately 23° C.), and tol is toluene.

In embodiments according to the present invention, a process for makinga poly alpha-olefin, PAO comprises contacting a feed containing a C₆-C₃₂alpha-olefin and optional ethylene with a catalyst system comprising ametallocene compound in a polymerization reactor under polymerizationconditions to effect a polymerization reaction to obtain apolymerization reaction mixture comprising vinylidenes, tri-substitutedvinylenes, and optionally di-substituted vinylenes, and optionallyvinyls; and obtaining an unsaturated PAO product from the polymerizationreaction mixture, wherein the polymerization reaction exhibits aselectivity toward greater than or equal to about 80 mol % vinylidenes,preferably 90 mol % vinylidenes, more preferably 96.5 mol % vinylidenes,based on total moles of vinyls, vinylidenes, di-substituted vinylenes,and tri-substituted vinylenes in the unsaturated PAO product; whereinthe metallocene compound is represented by formula (I):

wherein: each R¹, R², and R³ is, independently, hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group, preferably wherein a first one of R¹, R², and R³ is asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group; a second one of R¹, R², and R³ is hydrogen; and athird one of R¹, R², and R³ is hydrogen, a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl group; R⁶, R⁷,R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring; R¹², R¹³, R¹⁴ and R¹⁵ are eachindependently a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₂₀ hydrocarbyl group; R¹⁶ is a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl group orsilylcarbyl group; each X is independently a halogen, a hydride, anamide, an alkoxide, a sulfide, a phosphide, a diene, an amine, aphosphine, an ether, a C₁-C₂₀ substituted or unsubstituted linear,branched linear, or cyclic hydrocarbyl group, or two or more X moietiestogether form a fused ring or ring system; M is a group 3, 4 or 5transition metal having an integer coordination number of v, typically3, 4, or 5; and m is an integer equal to v-2, typically 1, 2, or 3.

In particular embodiments of the process, R² is hydrogen. Inembodiments, one of R¹ and R³ is a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₆ hydrocarbyl group, and the other one ofR¹ and R³ is a hydrogen.

In some embodiments, one or both of R¹ and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₆ hydrocarbylgroup.

In some embodiments one of R¹ and R³ comprise an alpha Group 14 atomdirectly attached to the indenyl ring, a beta Group 14 atom attached tothe alpha atom, and two or more, preferably three, substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroups attached to the beta atom.

In particular embodiments, the metallocene compound is represented byformula (II):

wherein: R¹ and R² are hydrogen; R²³ and R¹⁹ comprise Group 14 atoms,preferably C, Ge, or Si (preferably R²³ is C and R¹⁹ is C or Si); R²⁰,R²¹, and R²² are independently hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup and at least two of R²⁰, R²¹, and R²² are independently asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group, wherein at least two of R²⁰, R²¹, and R²² are asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group; R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen;a substituted or unsubstituted linear, branched linear, or cyclic C₁-C₃₀hydrocarbyl group; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, takentogether with the carbon atoms in the indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings annelated to the indenyl ring; R¹², R¹³, R¹⁴, R¹⁵,and R¹⁶ are each independently a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₈ hydrocarbyl group; each X isindependently a halogen, a hydride, an amide, an alkoxide, a sulfide, aphosphide, a diene, an amine, a phosphine, an ether, or a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system; M is a group 3, 4, or 5 transition metal having aninteger coordination number of v, such as 3, 4 or 5; and m is an integerequal to v-2, such as 1, 2 or 3.

In particular embodiments, R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, takentogether with the respective carbon atoms in the indenyl ring to whichthey are directly connected, form a ring annelated to the indenyl ring.In some embodiments, the ring annelated to the indenyl ring comprisesone or more saturated carbon atoms. In some embodiments, at least fourof R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroup, preferably methyl or ethyl.

In particular embodiments, R¹⁶ is a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₈ hydrocarbyl group, preferably methyl orethyl. In some embodiments, i) at least three of R¹², R¹³, R¹⁴, R¹⁵, andR¹⁶ if present are not hydrogen; ii) two or more of R¹², R¹³, R¹⁴, R¹⁵and R¹⁶ if present together form a fused ring or ring system; iii) atleast two of R⁶, R⁷, R¹⁷, and R¹⁸ are hydrogen; iv) each X isindependently a halogen or a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₆ hydrocarbyl group; v) M comprises Zr orHf; or a combination thereof.

In particular embodiments, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are eachindependently a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₈ hydrocarbyl group, preferably methyl or ethyl.

In particular embodiments the metallocene compound is represented byformula (I-B), (III-B), (IV-B), (VI), (VIII), (IX), (X), (XI), (XII),(XV), (XVII), (XVIII), or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched linear,or cyclic hydrocarbyl group, or two or more X moieties may together forma fused ring or ring system; M is Hf or Zr; and m is 2. In particularembodiments of the process, the metallocene is not represented byformula (I-B).

In some embodiments of the process, the polymerization reaction exhibitsa selectivity toward a combination of greater than or equal to about96.5 mol % vinylidenes, from 0.5 mol % to 3.5 mol % tri-substitutedvinylenes, less than or equal to about 1.5 mol % di-substitutedvinylenes, and less than or equal to about 1.5 mol % vinyls, based ontotal moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product.

In particular embodiments of the process, the polymerization reactionexhibits a selectivity toward a combination of vinylidenes of equal toor greater than 97.0 mol %, preferably equal to or greater than 97.9 mol%; tri-substituted vinylenes of less than 2.1 mol %; di-substitutedvinylenes of 0.5 mol % or less; and vinyls of 1.0 mol % or less, basedon total moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product. In particularembodiments of the process, the polymerization reaction exhibits aselectivity towards a combination of vinylidenes and tri-substitutedvinylenes of collectively greater than 98.0 mol %, preferably greaterthan 98.5 mol %, and a combination of di-substituted vinylenes andvinyls of collectively less than 2.0 mol %, preferably less than 1.5 mol%, based on total moles of vinyls, vinylidenes, di-substitutedvinylenes, and tri-substituted vinylenes in the unsaturated PAO product.

In some embodiments of the process the polymerization reaction resultsin the unsaturated PAO product having a number average molecular weight(Mn) of 1500 g/mol or less, preferably from 300 to 800 g/mol, asmeasured by ¹H NMR. In some embodiments, the catalyst system furthercomprises a non-coordinating anion type activator, preferably whereinthe non-coordinating anion type activator comprises: dimethylaniliniumtetrakisperfluorophenylborate, dimethylaniliniumtetrakisperfluoro-naphthylborate, triphenylcarboniumtetrakisperfluorophenylborate, triphenylcarboniumtetrakisperfluoronaphthylborate, dimethylaniliniumtetrakisperfluorophenylaluminate, dimethylaniliniumtetrakisperfluoronaphthylaluminate, or combinations thereof.

In particular embodiments of the process, the polymerization conditionscomprise a reaction temperature from 40° C. to 150° C.; an averageactivity level of at least 1200 g/s·mol; the polymerization reactionmixture exhibits an oligomer yield of at least 10%; or a combinationthereof.

In some embodiments the process further comprises: a) contacting theunsaturated PAO product with hydrogen to convert at least a portion ofthe unsaturated PAO product to a hydrogenated PAO product; b) contactingthe unsaturated PAO product with a chemical reagent to convert at leasta portion of the unsaturated PAO product to a functionalized PAOproduct; or a combination thereof.

In particular embodiments of the process, the feed comprises C₆-C₂₄alpha-olefin; and any combination of C₂-C₅ alpha-olefins arecollectively present in the alpha-olefin feed at no higher than 25 mol%, based on the total moles of the alpha-olefins supplied to thepolymerization reactor, preferably wherein the alpha-olefin feed issubstantially free of ethylene, propylene, C₄ alpha-olefins, and C₅alpha-olefins; or a combination thereof. Preferably, the alpha-olefinfeed is substantially free (preferably absent, 0 mol %) of propylene, C₄alpha-olefins, and C₅ alpha-olefins; or a combination thereof andoptionally comprises less than 25 mol % ethylene, preferably less than15 mol %, preferably less than 5 mol %.

In embodiments of the invention, an unsaturated poly alpha-olefinproduct comprises greater than or equal to about 80 mol % vinylidenes,preferably 90 mol % vinylidenes, more preferably 96.5 mol % vinylidenes,based on total moles of vinyls, vinylidenes, di-substituted vinylenes,and tri-substituted vinylenes contained therein. In particularembodiments the unsaturated poly alpha-olefin product comprises 96.5 mol% to 99.9 mol % of vinylidenes; 0.1 mol % to 3.5 mol % oftri-substituted vinylenes; 3.0 mol % or less of di-substitutedvinylenes; 3.0 mol % or less of vinyl groups; based on total moles ofvinylidenes, tri-substituted vinylenes, di-substituted vinylenes, andvinylidenes contained therein; and a number average molecular weight(Mn) of 1500 g/mol or less as measured by ¹H NMR.

In some embodiments the unsaturated poly alpha-olefin product comprisesless than or equal to about 1.0 mol % di-substituted vinylenes, whenpresent; less than or equal to about 1.0 mol % vinyl groups whenpresent; and a number average molecular weight (Mn) of 1000 g/mol orless as measured by ¹H NMR.

In particular embodiments, the unsaturated poly alpha-olefin productcomprises from 98 mol % to 99.5 mol % of a combination of vinylidenesand tri-substituted vinylenes; 0.5 mol % to 2 mol % of a combination ofdi-substituted vinylenes and vinyl groups, and a number averagemolecular weight (Mn) of 800 g/mol or less as measured by ¹HNMR.

In embodiments of the invention, a catalyst compound suitable to producean unsaturated PAO product from C₆-C₃₂ alpha-olefin under polymerizationconditions comprises a polymerization selectivity suitable to form anunsaturated PAO product comprising greater than or equal to about 80 mol% vinylidenes, preferably 90 mol % vinylidenes, more preferably 96.5 mol% vinylidenes, based on total moles of vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes in theunsaturated PAO product. In particular embodiments, the catalystcompound is represented by the formula (F-MC2):

in which one of R¹, R², and R³ is an alpha Group 14 atom directlyattached to the indenyl ring, and a beta Group 14 atom attached to thealpha atom, and two or more, preferably three, substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroups attached to the beta atom, optionally two of R¹, R², and R³ areeach hydrogen; R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently ahydrogen or a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₂₀ hydrocarbyl group; R¹², R¹³, R¹⁴, and R¹⁵ are eachindependently a hydrogen, or a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group; R¹⁶ is a hydrogen,a substituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group or silylcarbyl group; each X is independently ahalogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, adiene, an amine, a phosphine, an ether, or a C₁-C₂₀ substituted orunsubstituted linear, branched linear, or cyclic hydrocarbyl group, ortwo or more X moieties together form a fused ring or ring system; M is agroup 3, 4, or 5 transition metal having an integer coordination numberof v, such as 3, 4, or 5; and m is an integer equal to v-2, such as 1, 2or 3.

In particular embodiments, the catalyst compound comprises apolymerization selectivity suitable to form an unsaturated PAO productcomprising 96.5 mol % to 99.9 mol % of vinylidenes; 0.1 mol % to 3.5 mol% of tri-substituted vinylenes; 2.0 mol % or less of di-substitutedvinylenes; 2.0 mol % or less of vinyl groups; based on total moles ofvinyls, vinylidenes, di-substituted vinylenes, and tri-substitutedvinylenes in the unsaturated PAO product; and a number average molecularweight (Mn) of 1500 g/mol or less as measured by ¹H NMR.

In particular embodiments, the catalyst compound is represented byformula (I), (II), (F-MC2), or (IV):

wherein:

i) according to formula (I): a first one of R¹ and R³ is a substitutedor unsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; a second one of R¹, R², and R³ is a hydrogen; the third one ofR¹, R², and R³ is a hydrogen; R⁶, R⁷, R¹⁷, and R¹⁸ are eachindependently hydrogen, a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₃₀ hydrocarbyl group; and R R¹², R¹³, R¹⁴, R¹⁵,and R¹⁶ are each independently a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group or R¹⁶ may be asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀,preferably C₁-C₈, hydrocarbyl group or silylcarbyl group; or

ii) according to formula (II): R¹ and R² are hydrogen; R²³ and R¹⁹comprise Group 14 atoms, such as C, Ge, and Si; R²⁰, R²¹, and R²² areindependently hydrogen or a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group, wherein at leasttwo of R²⁰, R²¹, and R²² are a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group; R⁶, R⁷, R¹⁷, andR¹⁸ are each independently hydrogen, a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₃₀ hydrocarbyl group, or two ofR⁶, R⁷, R¹⁷, and R¹⁸ taken together with the carbon atoms in the indenylring to which they are directly connected, collectively form one or moresubstituted or unsubstituted rings annelated to the indenyl ring; andR¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; or

iii) according to formula (F-MC2): one of R¹ and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; two of R¹, R², and R³ are each hydrogen; R⁶, R⁷, R⁸, R⁹, R¹⁰, andR¹¹ are each independently hydrogen, a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₃₀ hydrocarbyl group, or two ofR⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ taken together with the carbon atoms in thebenzindenyl ring to which they are directly connected, collectively formone or more substituted or unsubstituted rings annelated to thebenz-indenyl ring; and R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are eachindependently a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₂₀ hydrocarbyl group; or

iv) according to formula (IV): one of R¹ and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; two of R¹, R², and R³ are each hydrogen; R⁶, R¹⁸, R²⁹, R²⁴, R²⁵,R²⁶, and R²⁷ are each independently hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup, or two of R⁶, R¹⁸, R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷ taken togetherwith the carbon atoms in the cyclopentan-indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings annelated to the cyclopentan-indenyl ring; and R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; wherein in the formulae (I), (II), (III), (IV): each X isindependently a halogen, a hydride, an amide, an alkoxide, a sulfide, aphosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system; M is a group 3, 4, or 5 transition metal having aninteger coordination number of v, such as 3, 4, or 5; and m is aninteger equal to v-2, such as 1, 2, or 3.

In particular embodiments, the catalyst compound comprises apolymerization selectivity suitable to form an unsaturated PAO productcomprising: greater than or equal to about 96.5 mol % vinylidenes; lessthan or equal to about 3.5 mol % tri-substituted vinylenes; less than orequal to about 1.0 mol % di-substituted vinylenes, when present; lessthan or equal to about 1.0 mol % vinyl groups when present; based ontotal moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; and a numberaverage molecular weight (Mn) of 1500 g/mol or less as measured by ¹HNMR.

In particular embodiments, the catalyst compound is represented byformula (III-B), (IV-B), (VI), (VIII), (IX), (X), (XI), (XII), (XV),(XVII) (XVIII) or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched linear,or cyclic hydrocarbyl group, or two or more X moieties may together forma fused ring or ring system; M is a group 3, 4, or 5 transition metalhaving an integer coordination number of v, such as 3, 4, or 5; and m isan integer equal to v-2, such as 1, 2 or 3.

I. Unsaturated PAO Product

PAOs are polymeric, typically oligomeric, molecules produced from thepolymerization reactions of alpha-olefin monomer molecules in thepresence of a catalyst system. An unsaturated poly alpha-olefin (uPAO)molecule in the material of the present invention contains a C═C bondtherein. Each uPAO molecule has a carbon chain with the largest numberof carbon atoms, which is designated the carbon backbone of themolecule. Any non-hydrogen group attached to the carbon backbone otherthan to the carbon atoms at the very ends thereof is defined as apendant group. The number of carbon atoms in the longest carbon chain ineach pendant group is defined as the length of the pendant group. Thebackbone typically comprises the carbon atoms derived from the C═C bondsin the monomer molecules participating in the polymerization reactions,and additional carbon atoms from monomer molecules and/or molecules inthe catalyst system that form the two ends of the backbone. A typicaluPAO molecule can be represented by the following formula (F-1):

where R¹, R^(2a), R^(2b), R³, each of R⁴ and R⁵, R⁶, and R⁷, the same ordifferent at each occurrence, independently represents a hydrogen or asubstituted or unsubstituted hydrocarbyl (preferably an alkyl) group,and n is a non-negative integer corresponding to the degree ofpolymerization. Where R¹, R^(2a) and R^(2b) are all hydrogen, (F-1)represents a vinyl uPAO; where R¹ is not hydrogen, and both R^(2a) andR^(2b) are hydrogen, (F-1) represents a vinylidene uPAO; where R¹ ishydrogen, and only one of R^(2a) and R^(2b) is hydrogen, (F-1)represents a di-substituted vinylene uPAO; and where R¹ is not hydrogen,and only one of R^(2a) and R^(2b) is hydrogen, then (F-1) represents atri-substituted vinylene uPAO.

Where n=0, (F-1) represents an uPAO dimer produced from the reaction oftwo monomer molecules after a single addition reaction between two C═Cbonds.

Where n=m, m being a positive integer, (F-1) represents a moleculeproduced from the reactions of m+2 monomer molecules after m+1 steps oflinear addition reactions between two C═C bonds.

Thus, where n=1, (F-1) represents a trimer produced from the reactionsof three monomer molecules after two steps of linear addition reactionsbetween two C═C bonds.

Assuming a carbon chain starting from R¹ and ending with R⁷ has thelargest number of carbon atoms among all straight carbon chains existingin (F-1), that carbon chain starting from R¹ and ending with R⁷ havingthe largest number of carbon atoms constitutes the carbon backbone ofthe unsaturated PAO product molecule (F-1). R², R³, each of R⁴ and R⁵,and R⁶, which can be substituted or unsubstituted hydrocarbyl(preferably alkyl) groups, are pendant groups (if not hydrogen).

If only alpha-olefin monomers are used in the polymerization process,and no isomerization of the monomers and oligomers ever occurs in thereaction system during polymerization, about half, typically at leastone more than half, of R¹, R^(2a), R^(2b), R³, all R⁴ and R⁵, R⁶, and R⁷would be hydrogen, and one of R¹, R^(2a), R^(2b), R⁶, and R⁷ would be ahydrocarbyl, such as methyl, and about half, typically less than half,of groups R¹, R^(2a), R^(2b), R³, all R⁴ and R⁵, R⁶, and R⁷ would behydrocarbyl groups introduced from the alpha-olefin monomer molecules.In a specific example of such case, assuming R^(2a) and R^(2b) arehydrogen, R³, all R⁵, and R⁶ are hydrogen, and R¹, all R⁴, and R⁷ have 8carbon atoms in the longest carbon chains contained therein, and n=8,then the carbon backbone of the (F-1) PAO molecule would comprise 35carbon atoms, and the average pendant group length of the pendant groups(the initial ═CR^(2a)R^(2b) group, and all of R⁴) would be 7.22 (i.e.,(1+8*8)/9). Such an uPAO molecule, which may be produced by polymerizing1-decene using certain metallocene catalyst systems, such as describedin greater detail below, can be represented by formula (F-2) below:

In such a molecule, the longest 5%, 10%, 20%, 40%, 50%, and 100% of thependant groups have average pendant group length of Lpg(5%) of 8,Lpg(10%) of 8, Lpg(20%) of 8, Lpg(50%) of 8, and Lpg(100%) of 7.22,respectively.

Depending on the polymerization catalyst system used, however, differentdegrees of isomerization of the monomers and/or oligomers can occur inthe reaction system during the polymerization process, resulting indifferent degrees of substitution on the carbon backbone. In a specificexample of such case, assuming R^(2a) and R^(2b) are both hydrogen, R³and all R⁵ are methyl, R⁶ is hydrogen, R¹ has 8 carbon atoms in thelongest carbon chain contained therein, all R⁴ and R⁷ have 7 carbonatoms in the longest carbon chain contained therein, and n=8, then thecarbon backbone of the (F-1) uPAO molecule would comprise 34 carbonatoms, and the average pendant group length of the pendant groups (theinitial ═CR^(2a)R^(2b) group, all R⁴, and R⁵) would be ˜3.7 (i.e.,(1+1+7*8+8*1)/18). Such an uPAO molecule, which may be produced bypolymerizing either 1-decene, with a given level and pattern ofisomerization, or by polymerizing a combination of 1-decene and2-decene, using certain non-metallocene catalyst systems, such asdescribed in greater detail below, can be represented by the followingformula (F-3):

In this molecule, the longest 5%, 10%, 20%, 40%, 50%, and 100% of thependant groups have average pendant group lengths of Lpg(5%) of 7,Lpg(10%) of 7, Lpg(20%) of 7, Lpg(50%) of 6.3, and Lpg(100%) of 3.7,respectively.

One skilled in the art, with knowledge of the molecular structure or themonomer(s) used in the polymerization step for making the unsaturatedPAO product, the process conditions (catalyst used, reaction conditions,etc.), and the polymerization reaction mechanism, inter alia, canapproximate the molecular structure of the uPAO molecules, thus thependant groups attached to the carbon backbone, and hence approximatevalues of Lpg(5%), Lpg(10%), Lpg(20%), Lpg(50%), and Lpg(100%),respectively.

One skilled in the art can determine the Lpg(5%), Lpg(10%), Lpg(20%),Lpg(50%), and Lpg(100%) values of a given unsaturated PAO product byusing separation and characterization techniques available to polymerchemists. For example, gas chromatography/mass spectroscopy machinesequipped with boiling point column separator can be used to separate andidentify individual chemical species and fractions; and standardcharacterization methods such as NMR, IR, and UV spectroscopy can beused to further confirm the structures.

The unsaturated PAO products of the present invention may be ahomopolymer made from a single alpha-olefin monomer or a copolymer madefrom a combination of two or more alpha-olefin monomers. In someembodiments, the alpha-olefin monomer(s) can include, consistessentially of, or be 1-hexene, 1-octene, 1-decene, 1-dodecene, or acombination thereof, such as 1-octene, 1-decene, and 1-dodecene.

The unsaturated PAO products of the present invention may be produced byusing a catalyst system comprising a specific type of metallocenecompound, such as described in detail below. The unsaturated PAOproducts can be substantially free of the alpha-olefin monomer(s), andmay advantageously contain vinylidenes at a high concentration,desirably in the range from c1 to c2 mol % in total, where c1 and c2 canbe, independently, 80, 85, 90, 91, 92, 93, 94, 95, 96, 96.5, 97, 98, 99,99.5, or 99.9, based on the total moles of vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes, as long asc1<c2. In particular embodiments, c1=90 and c2=99; c1=91 and c2=99;c1=92 and c2=98; c1=93 and c2=97; c1=96.5 and c2=99.9; or c1=98 andc2=99.5. Without intending to be bound by a particular theory, it isbelieved that the high concentrations of vinylidenes can be achievedpartly by the unique structure of the metallocene compound used in thecatalyst system.

Between the vinylidenes and tri-substituted vinylenes in the unsaturatedPAO product of the present invention, tri-substituted vinylenes tend tohave a considerably lower concentration than the vinylidenes. In someembodiments, the unsaturated PAO products of the present invention cancontain a concentration of tri-substituted vinylenes in the range fromc3 to c4 mol %, based on the total moles of the vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes, where c3 and c4can be, independently, 0, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0,4.5, 5.0, 5.5 or 6.0, as long as c3<c4. In particular embodiments,c3=0.5 and c4=5.5; c3=1.0 and c4=5.0; c3=0.5 and c4=4.0; c3=0 andc4=4.0; c3=0.1 and c4=3.5; or c3=0.5 and c4=2.

In some embodiments, the unsaturated PAO products of the presentinvention can desirably contain a high combined concentration ofvinylidenes and tri-substituted vinylenes, the combined concentrationbeing in the range from c5 to c6 mol %, based on the total moles of thevinyls, vinylidenes, di-substituted vinylenes, and tri-substitutedvinylenes, where c5 and c6 can be, independently, 85, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, or 99.5, based on the total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes, aslong as c5<c6. In particular embodiments, c5=90 and c6=99.5; c5=92 andc6=99.5; c5=94 and c6=99; c5=95 and c6=99; or c5=98 and c6=99.5.

Without intending to be bound by a particular theory, it is believedthat vinylidenes and tri-substituted vinylenes are more reactive thandi-substituted vinylenes when reacted with many functionalizing agents.Thus, the high concentration of vinylidenes, as well as the highcombined concentration of vinylidenes plus tri-substituted vinylenes, inthe unsaturated PAO products of the present invention may beparticularly advantageous if the unsaturated PAO products are used asintermediates for making functionalized PAO products.

The unsaturated PAO products of the present invention can desirablycontain di-substituted vinylenes at a low concentration in the rangefrom c7 to c8 mol %, based on the total moles of vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes, where c7 and c8can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1.0, 1.2, 1.4, 1.6,1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0, as long as c7<c8. Inparticular embodiments, c7=0 and c8=4.0; c7=0 and c8=3.0; c7=0 andc8=2.0; c7=0 and c8=1; c7=0 and c8=1.2; or c7=0.1 and c8=2.5. Withoutintending to be bound by a particular theory, it is believed that suchlow concentrations of di-substituted vinylenes in the unsaturated PAOproducts are achieved by the low selectivity toward these olefins in thepolymerization reactions, which can be enabled at least partially by theunique structure of the metallocene compound in the catalyst system usedin the polymerization reaction.

Depending on the metallocene compound used in the catalyst system, theunsaturated PAO products of the present invention can contain vinyls ata low concentration, e.g., from c9 to c10 mol %, based on the totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes, where c9 and c10 can be 0, 0.1, 0.2, 0.3,0.4, 0.5, 0.6, 0.7, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5,4.0, 4.5, or 5.0, as long as c9<c10. In particular embodiments, c9=0 andc10=4.0; c9=0 and c10=3.0; c9=0 and c10=2; c9=0 and c10=1.6; c9=0 andc10=1.0; or c9=0.1 and c10=1.2. Without intending to be bound by aparticular theory, it is believed that such low concentration of vinylsin the unsaturated PAO products are achieved by the low selectivitytoward vinyls in the polymerization reactions, which can be enabled bychoosing the molecular structure of the metallocene compound in thecatalyst system used in the polymerization reaction.

In some embodiments, the unsaturated PAO products of the presentinvention can desirably contain a low combined concentration of vinylsand di-substituted vinylenes, the combined concentration being in therange from c11 to c12 mol %, based on the total moles of the vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes,where c11 and c12 can be, independently, 0, 0.1, 0.2, 0.3, 0.4, 0.5,0.6, 0.7, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5,5.0, 5.5, or 6.0, as long as c11<c12. In particular embodiments, c11=0and c12=5.0; c11=0 and c12=4.0; c11=0.5 and c12=2; c11=0.5 and c12=4.5;or c11=0.8 and c12=5.0.

Thus, the unsaturated PAO products of the present invention cantypically comprise a plurality of PAO molecules, which may be the sameor different. Each uPAO molecule can comprise a plurality of pendantgroups, which may be the same or different, and the longest 5%, 10%,20%, 40%, 50%, and 100% of the pendant groups of all of the olefinmolecules of the unsaturated PAO product have an average pendent grouplength of Lpg(5%), Lpg(10%), Lpg(20%), Lpg(40%), Lpg(50%), andLpg(100%), respectively. It is preferred that at least one of thefollowing conditions are met:

-   -   (i) a1≤Lpg(5%)≤a2, where a1 and a2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0 15.5,        or 16.0, as long as a1≤a2;    -   (ii) b1≤Lpg(10%)≤b2, where b1 and b2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0,        as long as b1≤b2;    -   (iii) c1≤Lpg(20%)≤c2, where c1 and c2 can be, independently,        4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5,        10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or        15.0, as long as c1≤c2;    -   (iv) d1≤Lpg(40%)≤d2; where d1 and d2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0,        as long as d1≤d2;    -   (v) e1≤Lpg (50%)≤e2; where e1 and e2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, or 14.0, as long as        e1≤e2; and    -   (vi) f1≤Lpg(100%)≤f2, where f1 and f2 can be, independently,        4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5,        10.0, 10.5, 11.0, 11.5, 12.0, 12.5, or 13.0, as long as f1≤f2.

In some embodiments, at least 60% of the pendent groups on olefinmolecules in the unsaturated PAO product are straight chain alkylshaving at least 4 (e.g., at least 6, at least 8, or at least 10) carbonatoms. In particular embodiments, at least 90% of the pendent groups onthe olefin molecules in the unsaturated PAO product are straight chainalkyls having at least 4 (e.g., at least 6, at least 8, or at least 10)carbon atoms.

The unsaturated PAO products of the present invention may have variouslevels of regio-regularity. For example, each uPAO molecule may besubstantially atactic, isotactic, or syndiotactic. A category ofmetallocene compounds can lack C1, C2, and C₈ symmetry. Withoutintending to be bound by a particular theory, it is believed that PAOmaterials made by using such asymmetrical metallocene-based catalystsystem can tend to be atactic.

The unsaturated PAO products of the present invention can have viscosityvarying in a broad range. For example, the unsaturated PAO product mayhave a KV100 in a range from 1 to 5000 cSt, such as 1 to 3000 cSt, 2 to2000 cSt, 2 to 1000 cSt, 2 to 800 cSt, 2 to 600 cSt, 2 to 500 cSt, 2 to400 cSt, 2 to 300 cSt, 2 to 200 cSt, or 5 to 100 cSt. The exactviscosity of the unsaturated PAO product can be controlled by, e.g.,monomer used, polymerization temperature, polymerization reactorresidence time, catalyst used, concentration of catalyst used,distillation and separation conditions, and mixing multiple unsaturatedPAO products with different viscosity.

In addition, the unsaturated PAO products of the present inventionadvantageously have a low polydispersity index (PDI) in the range fromabout 1.0 to about 5.0 (e.g., from 1.2 to 4.0, from 1.3 to 3.0, from 1.4to 2.5, from 1.5 to 2.0, or from 1.6 to 1.8). A narrow molecular weightdistribution of the uPAO molecules can be achieved by usingmetallocene-compound-based catalyst systems in the polymerization stepunder controlled polymerization conditions (temperature fluctuation,residence time, and the like). Such narrow PDI is desirable in that itdefines a material with a high degree of homogeneity in molecularweight, molecular size, rheology behavior, viscosity index, anddegrading behavior (such as shear stability and oxidation stability).From an olefin mixture with such degree of homogeneity one can produce afunctionalized material having a similar degree of homogeneity as well.

In general, the olefin mixture in the unsaturated PAO products of thepresent invention can have an average molecular weight that can varywidely (and correspondingly, a KV100 that can vary widely). In someembodiments, the uPAO olefin mixture can have a number average molecularweight of Mn, where Mn1≤Mn≤Mn2, where Mn1 and Mn2 can be, independently,150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300,1400, 1500, 1700, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000,8,000, 9000, or 10000 g/mol, as long as Mn1<Mn2. In some embodiments,the uPAO olefin mixture can have a number average molecular weight of3000 g/mol or less, e.g., 2500 g/mol or less, 2000 g/mol or less, 1700g/mol or less, 1500 g/mol or less, 1400 g/mol or less, 1300 g/mol orless, 1200 g/mol or less, 1100 g/mol or less, 1000 g/mol or less, 900g/mol or less, 800 g/mol or less, 700 g/mol or less, 650 g/mol or less,620 g/mol or less, 600 g/mol or less, 520 g/mol or less, 500 g/mol orless, 400 g/mol or less, 380 g/mol or less, 370 g/mol or less, 360 g/molor less, 350 g/mol or less, 340 g/mol or less, 330 g/mol or less, or 320g/mol or less; typically, as the product is preferred to exclude olefinmonomers but may include dimers and higher mers, the number averagemolecular weight can optionally be at least 100 g/mol, e.g., at least150 g/mol or at least 200 g/mol, depending upon the molecular weight ofa monomeric feed olefin component.

The unsaturated PAO products of the present invention may additionallycomprise saturated hydrocarbons. The saturated hydrocarbons may beproduced in situ in the polymerization step of the alpha-olefin formaking the unsaturated PAO products, e.g., where the polymerization isconducted in the presence of a hydrogen-containing atmosphere.Alternatively or additionally, the saturated hydrocarbons may beproduced by a partial hydrogenation of a portion of the unsaturated PAOproduct as produced from the polymerization step. Further additionallyor alternatively, the saturated hydrocarbon may be blended with anolefin mixture to obtain a mixture of desired property and composition.Nonetheless, it is desired that the unsaturated PAO products of thepresent invention comprise the vinylidenes, tri-substituted vinylenes,optional vinyls and optional di-substituted vinylenes at a totalconcentration thereof of at least 50 wt % (e.g., at least 60, 65, 70,75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, or 99.8 wt %),based on total weight of the unsaturated PAO product.

In general, it is desired that the unsaturated PAO product of thepresent invention has a bromine number in a range from Nb(PAO)1 toNb(PAO)2, where Nb(PAO)1 and Nb(PAO)2 can be, independently, 1.0, 1.5,2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, or even 10.0,15.0, 10.0, as long as Nb(PAO)1<Nb(PAO)2. Desirably, a great majority,such as at least 80, 85, 90, 95, 98, or even 99 mol % of the moleculesin the unsaturated PAO product of the present invention may beunsaturated. Desirably, each unsaturated PAO molecule is capable ofaddition reaction with one Br₂ molecule to obtain a1,2-dibromo-derivative thereof.

Molecular structures of exemplary vinylidene uPAOs made from a mixtureof 1-octene and 1-dodecene alpha-olefin monomers at a molar ratio of 4:1can be schematically represented by formula (F-V) as follows, where ncan be any integer.

The two C₁₀ pendant groups are shown to be next to each other. In realmolecules, they may be randomly distributed among all of the pendantgroups. The structure shows nearly 100% isotacticity, i.e., 100 mol % of(m,m)-triads in the structure. In real molecules, a small fraction maybe (m,r)- or (r,r)-triads. Nonetheless, each of the long pendant groupscan extend to form a substantially linear chain, and interact with otherlong straight carbon chains from other uPAO molecules and othermolecules in its vicinity.

Because of the presence of the C═C bonds in the uPAO molecules, whenexposed to 02 molecules (such as when exposed to air), the unsaturatedPAO product can be oxidized if not protected by a more reactive materialtoward 02. To that end, in the unsaturated PAO products, anti-oxidantmaterials may be added to prolong shelf life and facilitate handling,storage, and transportation thereof. Such anti-oxidants can include, butare not limited to, those anti-oxidants typically used in lubricant basestocks and lubricating oil compositions. Non-limiting examples of suchanti-oxidants and the use quantity thereof are given in paragraphs[0101]-[0108], pages 9 and 10 of U.S. Patent Application Publication No.2010/0087349, the content of which is hereby incorporated by referencein its entirety.

II. Hydrogenation of the Unsaturated PAO Products

The unsaturated PAO products made by the method of the present inventioncan be directly used as a lubricating oil base stock and otherapplications because it can be made to have the desired physicalproperties, particularly rheological properties interesting for suchapplications. However, due to the presence of C═C bonds on a largeportion, if not all, of the uPAO molecules, direct use thereof as alubricating oil base stock can cause stability issues to the oil if theoil is exposed to an oxidative environment, such as the air. Thus, ingeneral, for lubricating oil applications, it may be desirable tohydrogenate the unsaturated PAO products to remove at least a portion,preferably a major portion, of the C═C bonds of the PAO molecules. Forexample, one can subject the unsaturated PAO product of the presentinvention to a step of hydrogenation by contacting it with ahydrogen-containing atmosphere in the presence of a hydrogenationcatalyst, such as one containing one or more of Fe, Co, Ni, preciousmetals (such as Ru, Rh, Pd, Os, Ir, Pt), and the like. Because of thecomposition of the unsaturated PAO product of the present invention,they can be advantageously hydrogenated to convert a great majority ofthe C═C bonds present in the olefin molecules into carbon-carbon singlebonds, thereby achieving a material that is substantially aliphatic andsaturated (e.g., which can be characterized by a low Bromine number ofno greater than 5.0, no greater than 4.0, no greater than 3.0, or nogreater than 2.0). Such hydrogenated, largely aliphatic hydrocarbonmaterials can have one or more of high viscosity index, low pour point,high oxidation stability, and high shear stability. They canadvantageously be used as, e.g., base stocks for lubricant compositions,such as those used in internal combustion engines, automotive greaseoils, industrial grease oils, gear box oils, and the like.

The hydrogenated PAO products made from hydrogenating the unsaturatedPAO products can generally exhibit viscosity, molecular weightdistribution, pendent group distribution, polydispersity index, that arealmost identical with those of precursor unsaturated PAO products. Thus,the hydrogenated PAO products of the present invention can have a KV100in a range from 1 to 5000 cSt, such as 1 to 3000 cSt, 2 to 2000 cSt, 2to 1000 cSt, 2 to 800 cSt, 2 to 600 cSt, 2 to 500 cSt, 2 to 400 cSt, 2to 300 cSt, 2 to 200 cSt, or 5 to 100 cSt.

The hydrogenated PAO products of the present invention canadvantageously have a low polydispersity index (PDI) in the range fromabout 1.0 to about 5.0 (e.g., from 1.2 to 4.0, from 1.3 to 3.0, from 1.4to 2.5, from 1.5 to 2.0, or from 1.6 to 1.8. Such narrow PDI can bedesirable, in that it defines a material with a high degree ofhomogeneity in molecular weight, molecular size, rheology behavior,viscosity index, and degrading behavior (such as shear stability andoxidation stability).

The hydrogenated PAO products of the present invention can have a numberaverage molecular weight of Mn, where Mn1≤Mn≤Mn2, where Mn1 and Mn2 canbe, independently, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000,1100, 1200, 1300, 1400, 1500, 1700, 2000, 2500, 3000, 3500, 4000, 4500,5000, 6000, 7000, 8,000, 9000, or 10000, as long as Mn1<Mn2. In someembodiments, the hydrogenated PAO product can have a number averagemolecular weight of 3000 g/mol or less, e.g., 2500 g/mol or less, 2000g/mol or less, 1700 g/mol or less, 1500 g/mol or less, 1400 g/mol orless, 1300 g/mol or less, 1200 g/mol or less, 1100 g/mol or less, 1000g/mol or less, 900 g/mol or less, 800 g/mol or less, 700 g/mol or less,600 g/mol or less, or 500 g/mol or less; typically, as the product ispreferred to exclude olefin monomers but may include dimers and highermers, the number average molecular weight can optionally be at least 100g/mol, e.g., at least 150 g/mol or at least 200 g/mol, depending uponthe molecular weight of a monomeric feed olefin component.

The hydrogenated PAO can be used as a high-quality API Group IV basestock. Various grades of the hydrogenated mPAO with KV100 varying fromvery low such as 1 cSt to very high such as 5,000 cSt can be made byusing the method of the present invention, and used for blending witheach other and other API Group I, II, III, IV, or V base stocks to makehigh-quality lubricating oil formulations, such as internal combustionengine oils, automobile drive line oils, industrial oils, greases, andthe like. Furthermore, the mPAO can be used as heat transfer oil (e.g.,transformer oil), processing oil, hydraulic power transfer oil, and thelike.

III. Functionalization of the Unsaturated PAO Products

The unsaturated PAO products of the present invention as describedabove, desirably produced by polymerization of alpha-olefin and/orolefinic monomers in the presence of a metallocene-compound-basedcatalyst system, can be advantageously used as a chemical intermediatefor making many products, especially those comprising a PAO moleculemoiety and one or more functional groups. The hydrocarbon molecules inthe unsaturated PAO products, if prepared from the polymerization ofolefins/alpha-olefins containing only one C═C double bond in theirpre-polymerized molecules, can tend to comprise no more than one C═Cbond each, with the rest of the molecular structure typically consistingof C—C bonds and C—H bonds.

The C═C bonds present in the molecules of the unsaturated PAO product ofthe present invention are highly reactive, and therefore can react withmultiple, different types of chemical agents having useful functionalgroups, thereby creating a PAO molecule further comprising a functionalgroup bonded thereto. The functional group can comprise, in turn, otherfunctional groups, which can react with additional chemical agents,bringing additional or different functional groups to the finalmolecule. The hydrocarbon substrate (i.e., the PAO structure) of thusfunctionalized PAO can impart desired properties to the functionalizedmaterial, such as solubility in organic media or hydrophobicity, and thefunctional groups can impart other desired properties to the finalmaterial, such as polarity, hydrophilicity (thus, solubility in aqueousmedia), and the like, making the final material particularly usefulwhere such dual properties are desired (e.g., detergents).

U.S. Publication No. 2014/0087986 discloses multiple methods for makingfunctionalized PAO from unsaturated PAO products produced bypolymerization of alpha-olefin monomers in the presence of ametallocene-compound-based catalyst system. The entirety of theinvention of this reference is incorporated by reference.

It is highly desired that upon functionalization of the unsaturated PAOproduct, the C═C double bond in the reacted uPAO molecule becomessaturated (i.e., each carbon atom in the original C═C bond is thenbonded to four atoms). This can be achieved by using functionalizationagents reactive substantially only toward the C═C bonds, butsubstantially inert toward the C—C bonds and C—H bonds in the uPAOolefin molecules under the functionalization conditions. Given that eachuPAO olefin molecule comprises typically only one C═C bond, the uPAOolefin molecule would then become saturated upon such functionalizationreaction.

Upon functionalization of the C═C bond in the uPAO olefin molecule, theoverall structure of the functionalized PAO molecule would besubstantially similar to that of a hydrogenated PAO molecule where theC═C bond has been saturated by hydrogenation as described above.Assuming that the bond between the functional group(s) to the carbonatom(s) is not significantly less robust than the C—C and C—H bonds, andassuming the functional group(s) per se are not significantly lessrobust than a pendant group on the PAO molecule under the useconditions, one can expect a stable oligomeric/polymeric structureretaining at least some of the interesting and useful properties of asaturated PAO molecule, such as one or more of viscosity index,oxidation stability, shear stability, Bromine number, and the like. Theretained properties can make the functionalized PAO materialparticularly useful in applications typical for the saturated PAOmaterials, such as lubricating oil compositions, and the like.

It is highly desirable that the functionalization agent used tofunctionalize the unsaturated PAO product is highly selective towardreacting with the C═C bond only, and is substantially inert with respectto the C—C bonds and C—H bonds on the uPAO molecules. This can ensurethe production of functionalized PAO molecules each comprising one ortwo functional group(s) only, and a complete functionalization ofsubstantially all of the uPAO molecules if desired. In applications suchas lubricating oil compositions, because of the high reactivity of C═Cbonds in the uPAO molecules, it may be desired that substantially all ofthe C═C bonds in the uPAO molecules are saturated before thefunctionalized PAO material is put into the oil compositions, either asa base stock or as an additive.

Additionally or alternatively, one may also functionalize the uPAOmolecules by substituting one or more of the hydrogen atoms on thecarbon backbone or one of the pendant groups with a functional group byusing chemical agents known to be reactive with C—H bonds. Because auPAO molecule typically comprise many C—H bonds at multiple locations,such reaction would be less selective than selective functionalizationof C═C bonds by using a functionalization agent that is inert to the C—Hbonds, and can result in very large number of very different molecules,and thus is less desirable than functionalization selective toward theC═C bonds only.

Additionally or alternatively, the uPAO products of the presentinvention can be functionalized by reaction between the unsaturated C═Cbonds of the uPAO molecules and a chemical reagent. The chemical reagentmay contain the moiety to be directly or indirectly reacted with thereactive portion(s) of the uPAO, optionally in the presence of anappropriate catalyst or facilitating agent. Alternatively, the chemicalreagent may be a precursor to be directly or indirectly reacted with thereactive portion(s) of the uPAO, optionally in the presence of anappropriate catalyst or facilitating agent, followed by at least oneother treatment and/or chemical reagent reaction, also optionally in thepresence of the same or a different appropriate catalyst or facilitatingagent, in order to effectuate a desired final functionality at thereactive portion(s) of the uPAO. Further alternatively, the chemicalreagent may be a co-reactant to be pre-reacted or simultaneously reactedwith another chemical reagent for direct or indirect reaction with thereactive portion(s) of the uPAO, optionally in the presence of anappropriate catalyst or facilitating agent.

Optionally, more than one type of functionality can be desired, suchthat the functionalization can occur simultaneously (effectuating avariety of functionalities in a single result), in series, in parallel(provided two parallel reactions do not countermand each other), or somecombination thereof. Whether one or more functionalities are desired,the reaction can be of any variety capable of effectively accomplishingthe functionalization, e.g., liquid-phase chemistry, gas-liquidinterfacial chemistry, solid-liquid surface chemistry, gaseousoxidation, gaseous oxidation followed by some other functionalizationmechanism, plasma oxidation, plasma oxidation followed by some otherfunctionalization mechanism, radical formation, radical formationfollowed by some other functionalization mechanism, or the like. Theultimately desired functional group(s) can be tailored to the particularend-use application, e.g., including but not limited to moietiescontaining an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorusatom, a boron atom, a silicon atom, a halogen atom, or a combinationthereof. The extent to which functionalization can be accomplished isanother variable that can be tailored to the particular end-useapplication. Functionalization (single or multiple) can be partial orsubstantially complete (i.e., in which substantially all theunsaturations of the uPAO can be converted into a functional moiety,such as a heteroatom-containing moiety).

IV. The Catalyst System

In embodiments, the catalyst system comprises a catalyst compound,preferably a metallocene compound which is activated by one or moreactivators. The catalyst system may further include a solvent, asupport, one or more scavengers, accelerators, and/or the like.

IV.1 the Metallocene Compound

The initial part to a catalyst system described herein is a metallocenecompound. The metallocene compound used in the process of the presentinvention for making PAOs generally has a structure represented byformula (F-MC) below comprising a first cyclopentadienyl ring withcarbon atoms directly connected with R¹, R², R³, R⁴, and R⁵, and asecond cyclopentadienyl ring with carbon atoms directly connected withR¹², R¹³, R¹⁴, R¹⁵, and R¹⁶.

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁ to C₂₀, preferablyC₁-C₈, hydrocarbyl group, wherein one of R¹, R², and R³ is a substitutedor unsubstituted linear, branched linear, or cyclic C₁ to C₂₀,preferably C₁-C₈, hydrocarbyl group, and optionally two of R¹, R², andR³ are each a hydrogen;

R⁴ and R⁵ are each independently a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₃₀ hydrocarbyl group, or R⁴ and R⁵, takentogether with the carbon atoms in the first cyclopentadienyl ring towhich they are directly connected, collectively form one or moresubstituted or unsubstituted rings annelated to the firstcyclopentadienyl ring;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁ toC₂₀, preferably C₁-C₈, hydrocarbyl group;

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branchedlinear, or cyclic C₁ to C₂₀, preferably C₁-C₈, hydrocarbyl group orsilylcarbyl group, preferably at least three (preferably at least four,preferably all five) of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are not hydrogen,optionally two or more of R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ moieties maytogether form a fused ring or ring system;

M is a group 3, 4, or 5 transition metal (preferably a group 4transition metal, preferably Hf, Ti, or Zr), having an integercoordination number of v, preferably v is 3, 4, or 5;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to v-2 (preferably m is 1, 2 or 3, preferably 2),preferably M is Zr or Hf, v is 4 and m is 2.

Preferably, in any formula herein, R² is hydrogen.

In some embodiments, preferred examples of C₁-C₂₀ and/or C₁-C₃₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl groups can include, but are not necessarily limited to:methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl,1-ethylethyl, n-pentyl, 1-methylpentyl, 1-ethylpropyl, 1-hexyl,1-methylpentyl, 1-ethylbutyl, 1-propylpropyl, optionally substitutedcyclohexyl, optionally substituted phenyl, optionally substitutedbenzyl, and the like, and any ethylenically unsaturated group that canbe derived from them by eliminating one available hydrogen group fromeach of two adjacent carbon atoms therein.

In some embodiments, M comprises, consists essentially of, or is Ti, Zr,and/or Hf. In a preferred embodiment, M comprises, consists essentiallyof, or is Zr and/or Hf. In some embodiments, the coordination number ofthe transition metal M is 4, and thus m is 2.

In some embodiments, each X is independently a halogen or a substitutedor unsubstituted linear, branched linear, or cyclic C₁-C₆ hydrocarbylgroup, e.g., a methyl, an ethyl, a propyl, a butyl, a phenyl, a benzyl,a chloride, a bromide, or an iodide.

Preferably, each R¹, R², and R³ is, independently, hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl).

In some embodiments, one of R¹, R², and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₆ hydrocarbyl group(e.g., a methyl, an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl,such as methyl), and (the other) two of R¹, R², and R³ are each ahydrogen.

In some embodiments, R¹ and R³ are each individually a substituted orunsubstituted linear, branched linear, or cyclic C₂-C₆ hydrocarbyl group(e.g., an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl), and R²is a hydrogen. In another embodiment, R¹ and R³ are each a methyl groupand R² is a hydrogen.

In some embodiments of the invention, one of R¹ and R³ is a tertiary orquaternary beta branched ligand in which the alpha and beta atoms are aGroup 14 atom, e.g., carbon, silicon, germanium, and two or more,preferably three, substituted or unsubstituted linear, branched linear,or cyclic C₁-C₁₈, preferably C₁-C₈, hydrocarbyl groups attached to thebeta atom. Examples include neopentyl, beta trialkylsilyl-methyl, andbeta-trialkylgermanyl-methyl moieties.

In some embodiments, R⁴ and R⁵, taken together with the carbon atoms inthe first cyclopentadienyl ring to which they are directly connected,collectively form a substituted or unsubstituted phenyl ring annelatedto the first cyclopentadienyl ring. In such embodiments, the four phenylring carbons not connected to the first cyclopentadienyl ring are eachindependently bonded to a hydrogen or a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₆ hydrocarbyl group (e.g., amethyl, an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl). In somesuch embodiments, at least two (e.g., at least three or all four) of thefour phenyl ring carbons not connected to the first cyclopentadienylring are connected to a hydrogen.

In some embodiments, R⁴ and R⁵, taken together with the carbon atoms inthe first cyclopentadienyl ring to which they are directly connected,collectively form a substituted or unsubstituted naphthenyl ringannelated to the first cyclopentadienyl ring. In any embodiment, theannelated ring or rings may comprise saturated ring carbons, unsaturatedring compounds, or a combination of saturated and unsaturated carbonatoms, for example, a non-aromatic ring or a combination of aromatic andnon-aromatic rings. In such embodiments, the metallocene compound canhave a structure represented by formula (F-MC2) below:

wherein R¹, R², R³, R¹², R¹³, R¹⁴, R, R¹⁶, M, X, v, and m are as definedin F-MC; and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently ahydrogen or a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, abutyl, a cyclohexyl, or a phenyl), optionally R¹ and R¹¹ are not bothhydrocarbyl groups.

In some embodiments of formula (F-MC2), at least two (e.g., at leastthree, at least four, at least five, or all six) of R⁶, R⁷, R⁸, R⁹, R¹⁰,and R¹¹ are a hydrogen.

Alternately, in some embodiments of formula (F-MC2), both R¹ and R¹¹ arehydrocarbyl, alternately C₁ to C₁₂ hydrocarbyl. Alternately, in someembodiments of formula (F-MC2), both R¹ and R¹¹ are not hydrocarbyl.

In some embodiments, the metallocene compound can have a structurerepresented by formula (F-MC2):

wherein:

R¹, R², R³, R¹⁶ are as defined in F-MC;

R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently a hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁ toC₂₀, preferably C₁-C₈, preferably C₁-C₆, hydrocarbyl group (e.g., amethyl, an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl),preferably R¹ and R¹¹ are not both hydrocarbyl groups; and one of R¹ andR³ is a substituted or unsubstituted linear, branched linear, or cyclicC₁-C₄ hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, or abutyl), or R² is a hydrogen, and either of R¹ and R³ is a hydrogen;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁ toC₂₀, preferably C₁-C₈, hydrocarbyl group (e.g., a methyl, an ethyl, apropyl, a butyl, a hexyl, an octyl, a cyclohexyl, a phenyl, or abenzyl),

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branchedlinear, or cyclic C₁ to C₂₀, preferably C₁-C₈, hydrocarbyl group (e.g.,a methyl, an ethyl, a propyl, a butyl, a hexyl, an octyl, a cyclohexyl,a phenyl, or a benzyl) or silylcarbyl group, preferably at least three(e.g., at least four or all five) of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are nothydrogen further, optionally two or more of R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶moieties may together form a fused ring or ring system;

M comprises, consists essentially of, or is Zr and/or Hf;

m is 2; and

each X is independently a methyl, an ethyl, a propyl, a butyl, a hexyl,an octyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide.

Both the first and second Cp rings in the metallocene compound of thepresent invention are substituted. One, but preferably not both, of thefirst and second Cp rings can be annelated to one or more rings.

This invention also relates to catalyst compounds represented by theformula:

wherein R¹, R³, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, M, X, v, and m are as definedfor F-MC, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined for F-MC2, and R²is hydrogen, or a substituted or unsubstituted linear, branched linear,or cyclic C₁-C₂₀, preferably C₂ to C₂₀, preferably C₂ to C₈, hydrocarbylgroup (preferably hydrogen).

Preferably, in any embodiment of any formula herein, M is Hf or Zr; m is2;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system (preferably each X is independently Cl,Br, Me, Et, Pr, or Bu);

one of R¹ and R³ is hydrogen and the other of R¹ and R³ is a substitutedor unsubstituted linear, branched linear, linear, or cyclic hydrocarbylgroup (preferably a C₁ to C₁₂ hydrocarbyl group, preferably a C₁ to C₄alkyl group, preferably methyl, ethyl, ethenyl and isomers of propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl)or a branching group;

R² is hydrogen, or a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₈ hydrocarbyl group (preferably a C₂ to C₆hydrocarbyl group, preferably a C₁ to C₄ alkyl group, preferably methyl,ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, or dodecyl);

R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently a hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₆hydrocarbyl group (preferably a C₁ to C₄ hydrocarbyl group, preferably aC₁ to C₄ alkyl group, preferably a C₁ to C₄ alkyl group, preferablymethyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, or dodecyl); and

R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₈hydrocarbyl group (preferably a C₁ to C₆ hydrocarbyl group, preferably aC₁ to C₄ alkyl group, preferably a C₁ to C₄ alkyl group, preferablymethyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), preferably at leastthree (preferably at least four, preferably all five) of R¹², R¹³, R¹⁴,R¹⁵ and R¹⁶ are not hydrogen optionally two or more of R¹², R¹³, R¹⁴,R¹⁵ and R¹⁶ moieties may together form a fused ring or ring system.

In a preferred embodiment in any formula described herein, R¹ ishydrogen and R³ is methyl, ethyl, ethenyl and isomers of propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl,preferably methyl.

In some embodiments, the metallocene compound used in the process of thepresent invention for making PAOs generally has a structure representedby formula (I) below comprising an indenyl ring with carbon atomsdirectly connected with R¹, R², R³, and a cyclopentadienyl ring withcarbon atoms directly connected with R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶:

wherein:

each R¹, R², and R³ is, independently, hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀, preferablyC₁-C₈, hydrocarbyl group, wherein a first one of R¹, R², and R³ is asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀,preferably C₁-C₈, hydrocarbyl group, a second one of R¹, R², and R³ ishydrogen; and the third one of R¹, R², and R³ is hydrogen, a substitutedor unsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup, or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring;

R¹², R¹³, R¹⁴ and R¹⁵ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

R¹⁶ is a substituted or unsubstituted linear, branched linear, or cyclicC₁-C₂₀ hydrocarbyl group or silylcarbyl group;

M is a transition metal, preferably a group 4 transition metal,preferably Hf, Ti, or Zr, having an integer coordination number of v,preferably v is 3, 4, or 5;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to v-2, preferably m is 1, 2 or 3, preferably 2,preferably M is Zr or Hf, v is 4 and m is 2.

Preferably, in any formula herein, R² is hydrogen.

In some embodiments, preferred examples of C₁-C₂₀ and/or C₁-C₃₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl groups can include, but are not necessarily limited to:methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl,1-ethylethyl, n-pentyl, neopentyl (2,2-methylpropyl), 1-methylpentyl,1-ethylpropyl, 1-hexyl, 1-methylpentyl, 1-ethylbutyl, 1-propylpropyl,optionally substituted cyclohexyl, optionally substituted phenyl,optionally substituted benzyl, and the like, and any ethylenicallyunsaturated group that can be derived from them by eliminating oneavailable hydrogen group from each of two adjacent carbon atoms therein.

In some embodiments, M comprises, consists essentially of, or is Ti, Zr,and/or Hf. In a preferred embodiment, M comprises, consists essentiallyof, or is Zr and/or Hf, preferably Hf. In some embodiments, thecoordination number of the transition metal M is 4, and thus m is 2.

In some embodiments, each X is independently a halogen or a substitutedor unsubstituted linear, branched linear, or cyclic C₁-C₆ hydrocarbylgroup, e.g., a methyl, an ethyl, a propyl, a butyl, a phenyl, a benzyl,a chloride, a bromide, or an iodide, preferably methyl.

Preferably, each R¹, R², and R³ is, independently, hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl), preferably subject to the proviso that atleast one of R¹, R², and R³ is a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀, preferably C₁-C₈, hydrocarbyl group,and two of R¹, R², and R³ are each hydrogen.

In some embodiments, one of R¹ and R³ is a beta branched ligand in whicha Group 14 atom, e.g., carbon, silicon, germanium, is attached directlyto the cyclopentadienyl ring, this same atom further includes at leasttwo non-hydrogen substituents according to the above listing. In otherwords, the Group 14 atom is tertiary or quaternarily substituted, whichincludes the bond between the cyclopentadienyl ring and the group 14atom. Examples include isobutyl, neopentyl, trialkylsilyl, andtrialkylgermanyl moieties according to formula (II)

wherein R²³ and R¹⁹ comprise Group 14 atoms, preferably carbon, siliconand/or germanium (preferably R²³ is C and R¹⁹ is C or Si), and at leasttwo of R²⁰, R²¹, and R²² are independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀, preferablyC₁-C₈, hydrocarbyl group.

In some embodiments, one of R¹, R², and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₆ hydrocarbyl group(e.g., a methyl, an ethyl, a propyl, a butyl, a pentyl, a neopentyl, anisoamyl, a cyclohexyl, or a phenyl, such as methyl), preferably a methylor a neopentyl, and the remaining two of R¹, R², and R³ are eachhydrogen.

In some embodiments, R⁶, R⁷, R¹⁷, and R¹⁸ are each independentlyhydrogen, a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₃₀ hydrocarbyl group. In some embodiments R⁶, R⁷, R¹⁷, andR¹⁸ are each independently hydrogen, a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₃₀ hydrocarbyl group in which twoof R⁶, R⁷, R¹⁷, and R¹⁸ taken together with the carbon atoms in theindenyl ring to which they are directly connected, collectively form oneor more substituted or unsubstituted rings annelated to the indenylring. The rings are indicated by the dotted lines between the respectiveR group substitutions with a ring between R⁶ and R⁷ indicated as Ring6-7, a ring between R⁷ and R¹⁷ indicated as Ring 7-17 and a ring betweenR¹⁷ and R¹⁸ indicated as Ring 17-18 as shown in the general formula(III-A) below:

In some embodiments, R⁶ and R⁷ taken together with the carbon atoms inthe indenyl ring to which they are directly connected, collectively formRing 6-7 comprising a C₃-C₆ ring, preferably an alicyclic ring,preferably a 5 membered ring including two the carbons of the indenylring. In such embodiments, the 3 alicyclic ring carbons not directlypart of the indenyl ring are each independently bonded to a hydrogen ora substituted or unsubstituted linear, branched linear, or cyclic C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl). In some embodiments, at least two or all threeof the alicyclic ring carbons are connected to a hydrogen, one of R¹ isa substituted or unsubstituted linear, branched linear, or cyclic C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, apentyl, an isoamyl, a neopentyl, a cyclohexyl, or a phenyl), and R² ishydrogen.

Preferably, at least one of R²⁰, R²¹, and R²² are C₁-C₆ hydrocarbylgroup (e.g., a methyl, an ethyl, a propyl, a butyl, a pentyl, anisoamyl, a neopentyl, a cyclohexyl, or a phenyl), such that R³ is abeta-branched moiety. In some embodiments, R²³ and R¹⁹ are carbon,silicon or germanium, and R²⁰, R²¹, and R²² are each a C₁-C₆ hydrocarbylgroup; preferably R²³ is a methylene group (—CH₂—) and R¹⁹, R²⁰, R²¹ andR²² form a trimethylsilyl, triethylsilyl, or terphenylsilyl moiety.Preferably in any of the above embodiments, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, and R¹⁸ are each independently a hydrogen, or a substituted orunsubstituted linear, or branched C₁-C₆, hydrocarbyl group. PreferablyR⁷ and R¹⁷ taken together with the carbon atoms in the indenyl ring towhich they are directly connected, collectively form Ring 7-17comprising three additional carbons to form a 5 membered alicyclic ring;R¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are methyl radicals, R², R³, R⁶, and R¹⁸,are hydrogen. In such embodiments, the metallocene compound can have astructure represented by formula (IV-B) below:

In some embodiments R¹⁷ and R¹⁸ taken together with the carbon atoms inthe indenyl ring to which they are directly connected, collectively formone or more substituted or unsubstituted C₃-C₆ rings annelated to theindenyl ring; and R⁶, R⁷, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are eachindependently a hydrogen, or a substituted or unsubstituted linear, orbranched C₁-C₆, hydrocarbyl group. Preferably R¹⁷ and R¹⁸ taken togetherwith the carbon atoms in the indenyl ring to which they are directlyconnected, collectively form a six membered phenyl ring, Ring 17-18comprising four additional carbons. In such embodiments, the four phenylring carbons not directly part of the indenyl ring (the carbons attachedto R⁸, R⁹, R¹⁰, and R¹¹ in formula (III) below) are each independentlybonded to a hydrogen or a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, an ethyl, apropyl, a butyl, a cyclohexyl, or a phenyl). In such embodiments, atleast two of, or at least three of, or all four of R⁸, R⁹, R¹⁰, and R¹¹are hydrogen. Stated another way, R¹⁷ and R¹⁸ taken together with thecarbon atoms in the first cyclopentadienyl ring to which they aredirectly connected, collectively form a substituted or unsubstitutednaphthenyl ring annelated to the first cyclopentadienyl ring. In suchembodiments, the metallocene compound can have a structure representedby formula (III) below:

Preferably in such an embodiment, one of R¹ and R²³ are a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₆ hydrocarbyl group(e.g., a methyl, an ethyl, a propyl, a butyl, a pentyl, an isoamyl, aneopentyl, a cyclohexyl, or a phenyl), R² and RI are hydrogen.Preferably in such an embodiment, R²³ and R¹⁹⁻²² form a neopentyl (i.e.,2,2-dimethylpropyl), R¹, R², R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are eachhydrogen, and R¹², R¹³, R⁴, R¹⁵, R¹⁶ are methyl; the metallocenecompound can have a structure represented by formula (III-B) below:

where M is Hf or Zr and M is 2.

Preferably, R²³, R¹⁹⁻²² form a methyl-trimethylsilyl,methyl-triethylsilyl, or methyl-triphenylsilyl moiety, R⁶, R⁷, R¹⁷, andR¹⁸, are each hydrogen, and or a substituted or unsubstituted linear, orbranched C₁-C₆, hydrocarbyl group. Preferably in such embodiments R⁶,R⁷, R¹⁷, and R¹⁸ are hydrogen, and R¹², R¹³, R¹⁴, R, R¹⁶ are methyl;having a structure represented by formula (III-SI) below.

wherein R²³, R²⁰, and R²¹ are substituted or unsubstituted linear,branched linear, or cyclic C₁-C₆ hydrocarbyl group, preferably methyl,ethyl, or phenyl, more preferably each of R²³, R²⁰, and R²¹ are methyl.

It is noted, in the embodiments listed above, R¹ and R³ may beinterchangeable. Reference to either of R¹ and R³ are maintained forconsistency and clarity herein. In any of the above embodiments, Mpreferably comprises, consists essentially of, or is Zr and/or Hf; m is2; and each X is independently a methyl, an ethyl, a propyl, a butyl, ahexyl, an octyl, a phenyl, a benzyl, a chloride, a bromide, or aniodide.

Particularly desirable metallocene compounds useful for the process ofthe present invention include the following compounds and their opticalisomers, if applicable (not shown):

Metallocene compounds generally can be synthesized by using typicalchemical reagents (e.g., halides of hafnium, zirconium, titanium) andintermediates (such as ligands containing one or two substituted orunsubstituted Cp rings, substituted or unsubstituted annelated Cp ringsuch as indenyl rings or benzindenyl rings, and the like) that arecommercially available, and following typical reaction schemesexemplified in various synthesis descriptions, e.g., as described in theexample sections of U.S. Provisional Application Nos. 62/477,683 and62/477,706, both filed Mar. 28, 2017, the contents of each of which arehereby incorporated by reference.

III.2 Activators and Activation of the Metallocene Compound

An additional component of a catalyst system described herein may be anactivator. The metallocene compounds, when activated by a commonly knownactivator such as non-coordinating anion activator, form activecatalysts for the polymerization or oligomerization of olefins.Activators that may be used include Lewis acid activators such astriphenylboron, tris-perfluorophenylboron, tris-perfluorophenylaluminumand the like and or ionic activators such as N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarboniumtetrakis(perfluorophenyl)borate, triphenylcarboniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)aluminate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)aluminate, and the like.

A co-activator is a compound capable of alkylating the transition metalcomplex, such that when used in combination with an activator, an activecatalyst is formed. Co-activators can include alumoxanes such asmethylalumoxane, modified alumoxanes such as modified methylalumoxane,and aluminum alkyls such trimethylaluminum, tri-isobutylaluminum,triethylaluminum, and tri-isopropylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tri-n-decylaluminum or tri-n-dodecylaluminum.Co-activators are typically used in combination with Lewis acidactivators and ionic activators when the pre-catalyst is not adihydrocarbyl or dihydride complex. Sometimes co-activators are alsoused as scavengers to deactivate impurities in feed or reactors.

U.S. Pat. No. 9,409,834 (e.g., at line 39, column 21 to line 44, column26) provides a detailed description of the activators and coactivatorsthat may be used with the metallocene compound in the catalyst system ofthe present invention. The relevant portions of this patent areincorporated herein by reference in their entirety.

Additional information of activators and co-activators that may be usedwith the metallocene compounds in the catalyst system of the presentinvention can be found in U.S. Patent Application Publication No.2013/0023633 (e.g., at paragraph [0178] page 16 to paragraph [0214],page 22). The relevant portions of this reference are incorporatedherein by reference in their entirety.

III.3 Scavenger

A scavenger can be an additional component of a catalyst systemdescribed herein. A scavenger is a compound typically added tofacilitate oligomerization or polymerization by scavenging impurities.Some scavengers may also act as activators and may be referred to asco-activators. A co-activator which is not a scavenger may also be usedin conjunction with an activator in order to form an active catalystwith a transition metal compound. In some embodiments, a co-activatorcan be pre-mixed with the transition metal compound to form an alkylatedtransition metal compound, also referred to as an alkylated catalystcompound or alkylated metallocene. To the extent scavengers facilitatethe metallocene compound in performing the intended catalytic function,scavengers, if used, are sometimes considered as a part of the catalystsystem.

U.S. Pat. No. 9,409,834 (e.g., at line 37, column 33 to line 61, column34) provides detailed description of scavengers useful in the process ofthe present invention for making PAO. The relevant portions in thispatent on scavengers, their identities, quantity, and manner of use areincorporated herein in their entirety.

IV. Process for Making PAO

The process for making a PAO of the present invention includes a step ofcontacting a feed comprising a C₆-C₃₂ alpha-olefin (preferably C₆-C₃₀,particularly C₆-C₂₄, C₆-C₁₈, C₈-C₁₈, or C₆-C₁₂) with a catalyst systemcomprising a metallocene compound described above in a polymerizationreactor under polymerization conditions to effect a polymerizationreaction to obtain a polymerization reaction mixture comprisingvinylidenes, ti-substituted vinylenes, optionally di-substitutedvinylenes, and optionally vinyls; and obtaining an unsaturated PAOproduct from the polymerization reaction mixture, wherein theunsaturated PAO product comprises vinylidenes, tri-substitutedvinylenes, optionally di-substituted vinylenes, and optionally vinyls.

IV.1 Monomer(s)

The alpha-olefin feed for making the PAO materials of the presentinvention may comprise one or more of C₆-C₃₂ alpha-olefins (preferablyC₆-C₂₄, particularly C₆-C₁₈, C₈-C₁₈, or C₆-C₁₂). Thus, the feed maycomprise ethylene, propylene, C₄ alpha-olefins, and C₅ alpha-olefins. Incertain embodiments, each of ethylene, propylene, C₄ alpha-olefins(1-butene and 2-methyl-1-propene), and C₅ alpha-olefins (1-pentene andvarious isomers of methyl-1-butene) is supplied to the polymerizationreactor, each independently at no higher than c1 mol %, based on thetotal moles of the alpha-olefins supplied to the polymerization reactor,where c1 can be 25, 20, 10, 5, 4, 3, 2, 1, 0.5, 0.1, or 0.01, for eachmonomer; additionally or alternatively, any combination of C₂-C₅alpha-olefins (including two or more, three or more, or all four ofethylene, propylene, C₄ alpha-olefins, and C₅ alpha-olefins) aresupplied to the polymerization reactor collectively at no higher than c1mol %, based on the total moles of the alpha-olefins supplied to thepolymerization reactor. Preferably, the alpha-olefin feed issubstantially free of ethylene, propylene, C₄ alpha-olefins, and C₅alpha-olefins (or completely free of intentionally added C₂-C₅alpha-olefins, allowing for impurities present in other feedcomponents). In preferable embodiments, substantially all alpha-olefinsin the feed are C₆-C₃₀ (e.g., C₆-C₂₄, particularly C₆-C₁₈, C₈-C₁₈, orC₆-C₁₂) alpha-olefins. “Substantially all” means at least 90 mol %(e.g., at least 92 mol %, at least 94 mol %, at least 95 mol %, at least96 mol %, at least 98 mol %, at least 99%, at least 99.5 mol %, orcompletely all, allowing for some impurities present in feedcomponents), based on the total moles of the alpha-olefins present inthe feed. Preferably, any combination of C₂-C₅ alpha-olefins arecollectively present in the alpha-olefin feed at no higher than c1 mol%, (where c1 can be 25, 20, 10, 5, 4, 3, 2, 1, 0.5, 0.1, or 0.01) basedon the total moles of the alpha-olefins supplied to the polymerizationreactor.

In some preferred embodiments, at least a portion (e.g., at least 80 mol%, at least 85 mol %, at least 90 mol %, at least 95 mol %, at least 96mol %, at least 98 mol %, at least 99%, at least 99.5 mol %, orcompletely all, allowing for some impurities present in feed components)of the alpha-olefins present in the feed are linear alpha-olefins(LAOs), i.e., those without a branch attached to the carbon backbonethereof. Non-limiting examples of LAOs are 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene, C₂₂, C₂₄, C₂₆,C₂₈, C₃₀ and C₃₂ LAOs. Without being bound by theory, PAO products madefrom such LAOs by using the process of the present invention can tend tohave fewer branches and pendant groups, leading to generally moreuniform PAO molecular structures, and hence typically better performancefor applications such as lubricant base stocks, lubricant additives, andthe like.

Where a single alpha-olefin is fed to the polymerization reactor, thethus obtained PAO is a homopolymer. Homopolymers can have substantiallyuniform molecular structure, and accordingly desirable physical andrheological properties such as viscosity index. A homopolymer can tendto have pendant groups attached to the carbon backbone with highlyuniform length.

In certain situations, a mixture of two, three, or even morealpha-olefins in the feed may be desired to produce a copolymer PAOproduct. To that end, alpha-olefins with the following combinations canbe particularly advantageous: C₆/C₈, C₆/C₁₀, C₆/C₁₂, C₆/C₁₄, C₆/C₁₆,C₈/C₁₀, C₈/C₁₂, C₈/C₁₄, C₈/C₁₆, C₁₀/C₁₂, C₁₀/C₁₄, C₁₀/C₁₆, C₁₀/C₁₈,C₁₂/C₁₄, C₁₂/C₁₆, C₁₂/C₁₈, C₁₂/C₂₀, C₆/C₈/C₁₀, C₆/C₈/C₁₂, C₆/C₈/C₁₄,C₆/C₁₀/C₁₂, C₆/C₁₀/C₁₄, C₈/C₁₀/C₁₂, C₈/C₁₀/C₁₄, C₈/C₁₂/C₁₄, C₁₀/C₁₂/C₁₆,C₁₀/C₁₂/C₁₈, C₁₀/C₁₄/C₁₆, C₁₀/C₁₄/C₁₈, and the like. Desirably, at leastone of the alpha-olefins in the mixture feed can be an LAO. Inparticular, substantially all of the alpha-olefins in the mixture feedcan be LAOs.

Preferred alpha-olefin monomers are mono-olefins containing one C═C bondper monomer molecule, though those olefins containing two or more C═Cbonds per monomer molecule can be used as well.

Preferred monomers useful herein include substituted or unsubstituted C₆to C₃₂ alpha olefins, or C₆ to C₂₀ alpha olefins, or C₆ to C₁₄ alphaolefins, or hexene, heptene, octene, nonene, decene, undecene, dodecene,tetradecene and isomers thereof. Preferably, the polyalphaolefinprepared herein comprises 50 mol % or more (preferably 60 mol % or more,preferably 70 mol % or more, preferably 80 mol % or more, preferably 90mol % or more, preferably 99 mol % or more) of one or more C₆ to C₃₂(preferably C₆ to C₂₀, preferably C₈ to C₁₈) alpha-olefin monomers.

Useful C₆ to C₃₂ alpha-olefin monomers include hexene, heptane, octene,nonene, decene, undecene, dodecene, tetradecene, substituted derivativesthereof, and isomers thereof.

Preferably, the monomers comprise C₆ to C₂₀ alpha-olefins, or C₆ to C₁₄alpha-olefins, and/or C₈ to C₁₂ alpha-olefins.

Preferred olefin monomers include one (alternately two, alternatelythree) or more of hexene, heptene, octene, nonene, decene, dodecene, andtetradecene.

In an embodiment the PAO is a homopolymer of any C₈ to C₁₂ alpha-olefin,i.e., the PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene or 1-tetradecene. Preferably,the PAO is a homopolymer of decene. In another embodiment the PAO is acopolymer comprising decene and one or more of any of the monomerslisted above.

In an embodiment, the PAO comprises two or more monomers, or three ormore monomers, or four or more monomers, or five or more monomers. Forexample, a C₈, C₁₀, C₁₂-linear alpha-olefin mixture, or a C₆, C₇, C₈,C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄-linear alpha-olefin mixture, or a C₆, C₈,C₁₀, C₁₂, C₁₄, C₁₆, C₁₈-linear alpha-olefin mixture can be used as afeed.

In an alternate embodiment, the PAO comprises less than 50 mol % of C₂,C₃, and C₄ monomers, or less than 40 mol %, or less than 30 mol %, orless than 20 mol %, or less than 10 mol %, or less than 5 mol %, or lessthan 3 mol %, or 0 mol %. Specifically, in an alternate embodiment, thePAO comprises less than 50 mol % of ethylene, propylene and butene, orless than 40 mol %, or less than 30 mol %, or less than 20 mol %, orless than 10 mol %, or less than 5 mol %, or less than 3 mol %, or 0 mol%. In another embodiment, the PAO comprises less than 40 mol %, or lessthan 20 mol %, or less than 10 mol %, or less than 5 mol %, or less than3 mol %, or 0 mol % of ethylene.

In an alternate embodiment, the PAO comprises less than 25 mol % of C₂,C₃, and C₄ monomers, or less than 20 mol %, or less than 15 mol %, orless than 10 mol %, or less than 5 mol %, or less than 1 mol %, or 0 mol%. Specifically, in an alternate embodiment, the PAO comprises less than25 mol % of ethylene, propylene and butene, or less than 20 mol %, orless than 15 mol %, or less than 10 mol %, or less than 5 mol %, or lessthan 1 mol %, or 0 mol %. In another embodiment, the PAO comprises lessthan 25 mol %, or less than 20 mol %, or less than 10 mol %, or lessthan 5 mol %, or less than 1 mol %, or 0 mol % of ethylene.

In another embodiment, the PAO comprises less than 40 mol % ofpropylene. In another embodiment, the PAO comprises less than 40 mol %of butene. In another embodiment, the PAO comprises less than 10 mol %of ethylene. In another embodiment, the PAO comprises less than 10 mol %of propylene. In another embodiment, the PAO comprises less than 10 mol% of butene.

In another embodiment, the PAO comprises less than 25 mol % ofpropylene. In another embodiment, the PAO comprises less than 25 mol %of butene. In another embodiment, the PAO comprises less than 5 mol % ofethylene. In another embodiment, the PAO comprises less than 5 mol % ofpropylene. In another embodiment, the PAO comprises less than 5 mol % ofbutene. In another embodiment, the PAO comprises less than 1 mol % ofethylene. In another embodiment, the PAO comprises less than 1 mol % ofpropylene. In another embodiment, the PAO comprises less than 1 mol % ofbutene.

The alpha-olefins used herein can be produced directly from ethylenegrowth process as practiced by several commercial production processes,or they can be produced from Fischer-Tropsch hydrocarbon synthesis fromCO/H₂ syngas, or from metathesis of internal olefins with ethylene, orfrom cracking of petroleum or Fischer-Tropsch synthetic wax at hightemperature, or any other alpha-olefin synthesis routes. An exemplaryfeed for this invention can be at least 80 wt % alpha-olefin (preferablylinear alpha olefin), preferably at least 90 wt % alpha-olefin(preferably linear alpha olefin), or approximately 100% alpha-olefin(preferably linear alpha olefin). However, alpha-olefin mixtures canalso be used as feeds in this invention, especially if the othercomponents are internal-olefins, branched olefins, paraffins, cyclicparaffins, aromatics (such as toluene and or xylenes). These componentsmay have diluent effects and are believed to not have a substantialdetrimental effect on the polymerization of alpha-olefins. In otherwords, the process described herein can selectively convertalpha-olefins in a mixture and leave the other components largely, ifnot completely, unreacted. This can be particularly useful when ethyleneis not present in the mixture. This technology can be used to separateout alpha-olefins from a mixture by selectively reacting them withpolymerization or oligomerization catalyst systems, effectively if notcompletely eliminating the need to separate alpha-olefins from theremainder of the components in a mixed feed stream. This can beeconomically advantageous, for example, in a process utilizingFisher-Tropsch synthesis olefin product streams containingalpha-olefins, internal-olefins and branched olefins. Such a mixture canbe fed to oligomerization technology as described herein and toselectively react away the alpha-olefin. No separate step to isolate thealpha-olefin may be needed. Another example of the utility of thisprocess involves alpha-olefins produced by the metathesis of internalolefins with ethylene, which may contain some internal olefins. Thismixed olefin base stock feed can be reacted as-is in thepolymerization/oligomerization process of the present invention, whichselectively converts the alpha-olefins into lube products. Thus, one canuse the alpha-olefin for the base stock synthesis without having toseparate the alpha-olefin from internal olefin. This can bring asignificant improvement in process economics. The feed olefins can bethe mixture of olefins produced from other linear alpha-olefin processcontaining C₄ to C₂₀ alpha-olefins as described in Chapter 3 “Routes toAlpha-Olefins” of the book Alpha Olefins Applications Handbook, Editedby G. R. Lappin and J. D. Sauer, published by Marcel Dekker, Inc. N.Y.1989.

IV.2 Feed Purification

Olefin feed and or solvents may be treated to remove catalyst poisons,such as peroxides, oxygen, or nitrogen-containing organic compounds oracetylenic compounds before being supplied to the polymerizationreactor. For example, the treatment of the linear alpha-olefin with anactivated 13A molecular sieve and a de-oxygenate catalyst (i.e., areduced copper catalyst) can increase catalyst productivity (expressedin terms of quantity of PAO produced per micromole of the metallocenecompound used) more than 10-fold. Alternatively, the feed olefins and orsolvents may be treated with an activated molecular sieve, such as 3 Å,4 Å, 8 Å, or 13 Å molecular sieve, and/or in combination with anactivated alumina or an activated de-oxygenate catalyst. Such treatmentcan desirably increase catalyst productivity 2- to 10-fold or more.

IV.3 Polymerization Reaction

Many polymerization/oligomerization processes and reactor types used formetallocene-catalyzed polymerization or oligomerization such assolution, slurry, and bulk polymerization or oligomerization processedcan be used in this invention. If a solid or supported catalyst is used,a slurry or continuous fixed bed or plug flow process may be suitable.Preferably, the monomers are contacted with the metallocene compound andthe activator in the solution phase, bulk phase, or slurry phase, forexample in a continuous stirred tank reactor or a continuous tubularreactor. In some embodiments, the temperature in any reactor used hereincan be from −10° C. to 250° C., e.g., from 30° C. to 220° C., preferablyfrom 50° C. to 180° C., from 60° C. to 170° C., or from 70° C. to 150°C. In some embodiments, the pressure in any reactor used herein can befrom 0.1 to 100 atmospheres, e.g., from 0.5 to 75 atmospheres or from 1to 50 atmospheres. Alternatively, the pressure is any reactor usedherein can be from 1 to 50,000 atmospheres, e.g., from 1 to 25,000atmospheres. Additionally or alternatively, the monomer(s), metalloceneand activator can be contacted for a residence time of 1 second to 100h, e.g., 30 seconds to 50 h, 2 minutes to 6 h, or 1 minute to 4 h.Additionally or alternatively, solvent or diluent may be present in thereactor and may include butanes, pentanes, hexanes, heptanes, octanes,nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes,pentadecanes, hexadecanes, toluene, o-xylene, m-xylene, p-xylene, mixedxylenes, ethylbenzene, propylbenzenes such as isopropylbenzene,butylbenzenes such as n-butylbenzene or t-butylbenzene, cumene, or acombination thereof, preferable solvents can include toluene, xylenes,ethylbenzene, normal paraffins (such as NORPAR® solvents available fromExxonMobil Chemical Company in Houston, Tex.), isoparaffin solvents(such as ISOPAR® solvents available from ExxonMobil Chemical Company inHouston, Tex.), and combinations thereof. These solvents or diluents maytypically be pre-treated in same manners as the feed olefins.

Regardless of the type of reactor or process, it is typically desirablethat the average activity level of the catalyst system be maintained ator above a sufficiently high level, so as to attain a minimum reasonableyield of oligomeric product, relative to monomeric reactant(s). Forexample, in some embodiments, the catalytic reaction can have an averageactivity level of at least 800 g/s·mol, e.g., at least 900 g/s·mol, atleast 1000 g/s·mol, at least 1100 g/s·mol, at least 1200 g/s·mol, atleast 1300 g/s·mol, at least 1400 g/s·mol, at least 1500 g/s·mol, atleast 1700 g/s·mol, at least 1900 g/s·mol, at least 2100 g/s·mol, atleast 2500 g/s·mol, or at least 2800 g/s·mol; although average activitylevels are not often characterized as being “too high,” it istheoretically possible for the average activity level to be so high thatcontrol of the reaction product may be difficult to achieve in practice,such that the average catalytic reaction activity level can optionallybe less than 1000 kg/s·mol, e.g., less than 500 kg/s·mol, in someembodiments. Additionally or alternatively, in some embodiments, thecatalytic reaction can provide a minimum reasonable yield (grams ofoligomer per grams of monomer feed) of at least 18%, e.g., at least 19%,at least 20%, at least 22%, at least 24%, at least 27%, at least 30%, atleast 33%, at least 36%, at least 38%, or at least 40%, based on areaction time of ˜1 h (˜3600 s); although reasonable catalytic yield isnot often characterized as being “too high,” with a maximum ofapproximately 100% in a 1-h reaction time, it is theoretically possiblefor relatively high yields, particularly high yields in relatively shortreaction times, to detrimentally affect the ability to control thereaction product, e.g., such that a maximum reasonable yield mayoptionally be approximately 100% in a reaction time of ˜1 minute orless, e.g., approximately 100% in a reaction time of ˜10 minutes orless, approximately 100% in a reaction time of ˜30 minutes or less,approximately 100% in a reaction time of ˜1 h or less, approximately 95%in a reaction time of ˜1 h or less, or approximately 90% in a reactiontime of ˜1 h or less.

In some embodiments, it can be desirable to attain both relatively lowproduct molecular weight and relatively high product vinylidene content.However, in many metallocene reactions where a vinylidene bond is asignificant unsaturation product (at least 30 mol %, relative to thetotal number of moles of vinyls, vinylidenes, di-substituted vinylenes,and tri-substituted vinylenes), increasing reaction temperature cancause a decrease (or at least no increase) in both molecular weight andvinylidene content. Because reaction temperature can be one of the mostubiquitous ways to control product characterization parameters for agiven catalyst system, it can often be a challenge to attain a producthaving both relatively low molecular weight and relatively highvinylidene content in many conventional systems. Thus, in some preferredembodiments of the invention, the combination of thereaction/polymerization/oligomerization conditions with certainmetallocene catalyst systems can advantageously result in bothdecreasing molecular weight and increasing vinylidene content withincreasing reaction temperature, thereby allowing heightened control ofdesired parameters without having to sacrifice one too much to attainthe other. In such preferred embodiments, e.g., by carefully selectingthe elements of the metallocene catalyst system, the average activitylevel of the catalyst system be can be further advantageously maintainedat or above a sufficiently high level, so as to attain a minimumreasonable yield of oligomeric product, relative to monomericreactant(s).

Typically, one or more metallocene compounds, one or more activators,and one or more monomers are contacted to produce polymer or oligomer.These catalysts may be supported and, as such, may be particularlyuseful in the known slurry, solution, or bulk operating modes conductedin single, series, or parallel reactors. If the catalyst, activator, orco-activator is a soluble compound, the reaction can be carried out in asolution mode. Even if one of the components is not completely solublein the reaction medium or in the feed solution, either at the beginningof the reaction or during or at later stages of the reaction, a solutionor slurry type operation may still be applicable. In any instance, thecatalyst system components, dissolved or suspended insolvents, such astoluene or other conveniently available aromatic solvents, or inaliphatic solvent, or in the feed alpha-olefin stream, can be fed intothe reactor under inert atmosphere (usually nitrogen or argon blanketedatmosphere) to allow the polymerization or oligomerization to takeplace.

The polymerization or oligomerization can be run in a batch mode, whereall the components are added into a reactor and allowed to react to apre-designed degree of conversion, either to partial conversion or fullconversion. Subsequently, the catalyst can be deactivated by anypossible means, such as exposure to air or water, or by addition ofalcohols or solvents containing deactivating agents.

The polymerization or oligomerization can additionally or alternativelybe carried out in a semi-continuous operation, where feeds and catalystsystem components can be continuously and/or simultaneously added to thereactor so as to maintain a constant ratio of catalyst system componentsto feed olefin(s). When all feeds and catalyst system components areadded, the reaction may be allowed to proceed to a pre-determined stage.The reaction can then be discontinued by catalyst deactivation in thesame manner as described for batch operation.

The polymerization or oligomerization can additionally or alternativelybe carried out in a continuous operation, where feeds and catalystsystem components can be continuously and/or simultaneously added to thereactor so to maintain a constant ratio of catalyst system and feedolefins. The reaction product can be continuously withdrawn from thereactor, as in a typical continuous stirred tank reactor (CSTR)operation. The residence times of the reactants can be controlled by apre-determined degree of conversion. The withdrawn product can thentypically be quenched in the separate reactor in a similar manner asother operation. In some embodiments, any of the processes to preparePAOs described herein are continuous processes, which can include thesteps of a) continuously introducing a feed stream comprising at least10 mol % of the one or more C₆ to C₂₄ alpha-olefins into a reactor, b)continuously introducing the metallocene compound and the activator intothe reactor, and c) continuously withdrawing the PAO from the reactor.Additionally or alternatively, the continuous process can include thestep of maintaining a partial pressure of hydrogen in the reactor of 200psig (˜1.4 MPag) or less, based upon the total pressure of the reactor,e.g., 150 psig (˜1.0 MPag) or less, 100 psig (˜690 kPag) or less, 50psig (˜350 kPag) or less, 25 psig (˜170 kPag) or less, or 10 psig (˜69kPag) or less. Additionally or alternatively the hydrogen, if present inthe reactor, in the feed, or in both, at a concentration of 1000 ppm orless by weight, e.g., 750 wppm or less, 500 wppm or less, 250 wppm orless, 100 wppm or less, 50 wppm or less, 25 wppm or less, 10 wppm orless, or 5 wppm or less.

Preferred reactors can range in size from 2 mL and up. Usually, it ispreferable to use reactors larger than one liter in volume forcommercial production. The production facility may have one singlereactor, or several reactors, arranged in series or in parallel or inboth to maximize productivity, product properties, and general processefficiency. The reactors and associated equipment are usuallypre-treated to ensure proper reaction rates and catalyst performance.The reaction is usually conducted under inert atmosphere, where thecatalyst system and feed components may be out of contact with anycatalyst deactivator or poison, e.g., polar oxygen, nitrogen, sulfur,and/or acetylenic compounds.

One or more reactors in series or in parallel may be used in the presentinvention. The metallocene compound, activator and when required,co-activator, may be delivered as a solution or slurry in a solvent orin the alpha-olefin feed stream, either separately to the reactor,activated in-line just prior to the reactor, or pre-activated and pumpedas an activated solution or slurry to the reactor.Polymerizations/oligomerization can be carried out in either singlereactor operation, in which monomer, or several monomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers may be added continuously to a single reactor or in seriesreactor operation, in which the above components can be added to each oftwo or more reactors connected in series. The catalyst system componentscan be added to the first reactor in the series. The catalyst systemcomponent may alternatively be added to both reactors, with onecomponent being added to first reaction and another component to otherreactors. In some embodiments, the metallocene compound can be activatedin the reactor in the presence of olefin. Alternatively, the metallocenecompound (such as a dichloride form of the metallocene compound) may bepre-treated with an alkylaluminum reagent, especiallytriisobutylaluminum, tri-n-hexylaluminum, and/or tri-n-octylaluminum,followed by charging into the reactor containing other catalyst systemcomponent and the feed olefins, or followed by pre-activation with theother catalyst system component to give the fully activated catalyst,which can then be fed into the reactor containing feed olefins. Inanother alternative, the pre-catalyst metallocene can be mixed with theactivator and/or the co-activator, and this activated catalyst can thenbe charged into reactor, together with feed olefin stream containingsome scavenger or co-activator. In another alternative, the whole orpart of the co-activator can be pre-mixed with the feed olefins andcharged into the reactor at the same time as the other catalyst solutioncontaining metallocene and activators and/or co-activator.

The catalyst compositions can be used individually or can be mixed withother known polymerization catalysts to prepare polymer or oligomerblends. Monomer and catalyst selection can allow polymer or oligomerblend preparation under conditions analogous to those using individualcatalysts. Polymers having increased PDI are available from polymersmade with mixed catalyst systems and can thus be achieved. Mixedcatalyst can comprise two or more metallocene compounds and or two ormore activators.

The PAOs described herein can additionally or alternatively be producedin homogeneous solution processes. Generally, this involvespolymerization or oligomerization in a continuous reactor in which thepolymer formed and the starting monomer and catalyst materials suppliedmay be agitated to reduce or avoid concentration or temperaturegradients. Temperature control in the reactor can generally be obtainedby balancing the heat of polymerization and with reactor cooling byreactor jackets or cooling coils or a cooled side-stream of reactant tocool the contents of the reactor, auto refrigeration, pre-chilled feeds,vaporization of liquid medium (diluent, monomers, or solvent) orcombinations of the above. Adiabatic reactors with pre-chilled feeds mayadditionally or alternatively be used. The reactor temperature may varywith the catalyst used and the product desired. Higher temperatures cantend to give lower molecular weights, and lower temperatures can tend togive higher molecular weights; however, this is not a fixed rule. Ingeneral, the reactor temperature preferably can vary between about 0° C.and about 300° C., e.g., from about 10° C. to about 230° C. or fromabout 25° C. to about 200° C. Usually, it is important to control thereaction temperature as pre-determined. In order to produce fluids withnarrow polydispersity, such as to promote the highest possible shearstability, it can be useful to control the reaction temperature toobtain minimum of temperature fluctuation in the reactor or over thecourse of the reaction time. If multiple reactors are used in series orin parallel, it may be useful to keep the temperature constant in apre-determined value, e.g., to minimize any broadening of molecularweight distribution. In order to produce a product with broadermolecular weight distribution, one can adjust the reaction temperatureswing or fluctuation, or, as in series operation, the second reactortemperature may be higher than the first reactor temperature. Inparallel reactor operation, the temperatures of the two reactors may beindependent. Or one can use more than one type of metallocene catalyst.

The pressure in any reactor used herein can vary from about 0.1atmosphere to about 100 atmospheres (about 1.5 psia to about 1500 psia),e.g., from about 0.5 atm to about 80 atm (˜7 psia to ˜1200 psia) or fromabout 1.0 atm to about 50 atm (˜15 psia to ˜750 psia). The reaction canbe carried out under an atmosphere of nitrogen or with some hydrogen.Sometimes a small amount of hydrogen may be added to the reactor toimprove catalyst performance. When present, the amount of hydrogen canbe kept at such a level to improve catalyst productivity, but preferablynot induce too much (preferably any significant) hydrogenation ofolefins, especially the feed alpha-olefins (the reaction ofalpha-olefins into saturated paraffins can be very detrimental to theefficiency of the process). The amount of hydrogen partial pressure isthus preferred to be kept low, e.g., less than 50 psi (350 kPa), lessthan 25 psi (170 kPa), less than 10 psi (69 kPa), or less than 5 psi (35kPa); additionally or alternatively, the concentration of hydrogen inthe reactant phase, in the reactor and/or feed, can be less than 10,000ppm (by wt.), e.g., less than 1000 ppm, less than 500 ppm, less than 100ppm, less than 50 ppm, less than 25 ppm, or less than 10 ppm.

The reaction time or reactor residence time can depend on the catalystused, the amount of catalyst used, and the desired alpha-olefinconversion level. Different metallocene compounds typically havedifferent activities. Usually, a higher degree of alkyl substitution onthe Cp ring, or bridging can improve catalyst productivity. High amountsof catalyst loading can tend to give higher alpha-olefin conversion atshorter reaction times. However, high amount of catalyst usage can makethe production process uneconomical and difficult to manage the reactionheat or to control the reaction temperature. Therefore, it can be usefulto choose a catalyst with maximum catalyst productivity to minimize theamount of metallocene and activator needed. When the catalyst system isa metallocene plus methylalumoxane, the range of methylalumoxane usedcan be in the range of 0.1 milligram/gram (mg/g) to 500 mg/g ofalpha-olefin feed, e.g., from 0.05 mg/g to 10 mg/g. Furthermore, themolar ratios of the aluminum to metallocene (Al/M molar ratio) can rangefrom 2 to 4000, e.g., from 10 to 2000, from 50 to 1000, or from 100 to500. When the catalyst system is a metallocene plus a Lewis Acid or anionic promoter with NCA component, the metallocene use can be in therange of 0.01 microgram/gram (mcg/g) to 500 mcg/g of metallocenecomponent relative to alpha-olefin feed, e.g., from 0.1 mcg/g to 100mcg/g, and/or the molar ratio of the NCA activator to metallocene can bein the range from 0.1 to 10, e.g., from 0.5 to 5 or from 0.5 to 3. If aco-activator of alkylaluminum compound is used, the molar ratio of theAl to metallocene can be in the range from 1 to 1000, e.g., from 2 to500 or from 4 to 400.

Typically, it can be preferable to have the highest possiblealpha-olefin conversion (close to 100%) of feed alpha-olefin in shortestpossible reaction time. However, in CSTR operation, sometimes it can bebeneficial to run the reaction at an optimum alpha-olefin conversion,which can be less than 100% alpha-olefin conversion, but preferablyclose to 100%. There are also occasions, when partial alpha-olefinconversion can be more desirable, e.g., when a narrow product PDI isdesirable, because partial conversion can avoid a PDI broadening effect.If the reaction is conducted to less than 100% conversion of thealpha-olefin, the unreacted starting material after separation fromother product and solvents/diluents can be simply removed, or may berecycled to increase the total process efficiency. Conversion, alsocalled alpha-olefin conversion, is determined by dividing the amount(grams) of isolated PAO recovered from the polymerization mixture (afterthe polymerization has been stopped) by the amount (grams) ofalpha-olefin introduced into the reactor. (When reported in %,conversion=(grams isolated PAO/grams alpha-olefin used)×100). Preferablythe conversion for the polymerization reactions described herein is 20%or more, alternatively 40% or more, alternatively 60% or more,alternatively 70% or more, alternately 80% or more, alternately 90% ormore, alternately 95% or more. Isolated PAO is the PAO product obtainedafter solvent, unreacted monomer and other volatiles (such as dimer)have been removed (such as by vacuum flash).

Desirable residence times for any process described herein can be from 1minute to 20 h, e.g., from 5 minutes to 10 h.

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The process can be carried out in acontinuous stirred tank reactor or plug flow reactor, or more than onereactor operated in series or parallel. These reactors may or may nothave internal cooling and the monomer feed may or may not berefrigerated. See the general invention of U.S. Pat. No. 5,705,577 forgeneral process conditions.

When a solid supported catalyst is used, a slurrypolymerization/oligomerization process generally operates in the similartemperature, pressure, and residence time range as described previously.In a slurry polymerization or oligomerization, a suspension of solidcatalyst, promoters, monomer and comonomers are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor. The catalyst is then separated from the product by filtration,centrifuge, or settlement. The fluid is then distilled to removesolvent, any unreacted components and light product. A portion or all ofthe solvent and unreacted component or light components can be recycledfor reuse.

If the catalyst used is un-supported or is a solution catalyst, when thereaction is complete or when the product is withdrawn from the reactor(such as in a CSTR), the product may still contain soluble, suspended,or mixed catalyst system components. These components can preferably bedeactivated and/or removed. Any of the usual catalyst deactivationmethods or aqueous wash methods can be used to remove the catalystsystem component. Typically, the reaction can be deactivated by additionof stoichiometric amount or excess of air, moisture, alcohol,isopropanol, etc. The mixture can then be washed with dilute sodiumhydroxide or with water to remove catalyst system components. Theresidual organic layer may then be subjected to distillation to removesolvent, which can optionally be recycled for reuse. The distillationcan further remove any light reaction product, e.g., from C₁₈ and less.These light components can be used as diluent for further reaction orcan be used as olefinic raw material for other chemical synthesis, asthese light olefin by-products may have vinylidene unsaturation, mostsuitable for further functionalization to convert in high performancefluids. Additionally or alternatively, these light olefin products canbe hydrogenated to be used as high quality paraffinic solvents.

Polymerization or oligomerization in absence of hydrogen may beadvantageous to provide polymers or oligomers with high degree ofunsaturated double bonds. These double bonds can be easily convertedinto functionalized fluids with multiple performance features. Examplesfor converting oligomers and/or polymers can be found in preparation ofashless dispersants, e.g., by reacting the polymers with maleicanhydride to give PAO-succinic anhydride which can then reacted withamines, alcohols, and/or polyether alcohols to convert into dispersants,such as disclosed in the book “Lubricant Additives: Chemistry andApplication,” ed. By Leslie R. Rudnick, p. 143-170.

Desirably, in the process of the present invention, due to the structurefeatures of the metallocene compound, the polymerization reactionmixture exiting the polymerization reactor can typically compriseoligomers including vinylidenes, tri-substituted vinylenes, optionallydi-substituted vinylenes, and optionally vinyls, optionally residualolefin monomer feed, optionally solvents, and components derived fromthe catalyst system.

The polymerization reaction mixture can then be quenched, e.g., by theaddition of a quenching agent such as water, CO₂, methanol, ethanol,mixtures thereof, and the like. Subsequently, the polymerizationreaction mixture can be separated to remove the residual monomer, whichcan be recycled to the polymerization reactor. Monomer removal can becarried out by means such as flashing under vacuum, distillation, orextraction. The resultant mixture can comprise an unsaturated PAOproduct including vinylidenes, tri-substituted vinylenes, optionallydi-substituted vinylenes, and optionally vinyls.

Without being bound by theory, it is believed that, a non-coordinatinganion with a large molecular size (e.g., dimethylaniliniumtetrakisperfluoronaphthylborate) can tend to result in higherselectivity toward vinyls and a lower selectivity toward vinylidenes, ascompared to non-coordinating anions with a small molecular size (e.g.,dimethylanilinium tetrakisperfluorophenylborate) when used as theactivator for the same metallocene compound of the present invention.

The unsaturated PAO product obtained immediately after monomer removalcan contain dimers, trimers, tetramers, pentamers, and even oligomerswith a higher degree of polymerization. Extraction or fractionation maybe carried out to separate the product into multiple fractions withdiffering boiling point ranges, corresponding to differing molecularweight range and differing degree of polymerization. For example, dimerscan be separated out as a low-viscosity, low boiling point fraction asone grade of product, and the residual material may be used as anotherunsaturated PAO product grade.

IV.6 Hydrogenation

At least a portion of the unsaturated PAO product can be hydrogenated toobtain an at least partly saturated PAO product. The unsaturated PAOproduct may be treated to reduce heteroatom-containing compounds to lessthan 600 ppm by wt. Thereafter, in some embodiments, the treated productcan then be contacted with hydrogen and a hydrogenation catalyst toproduce an at least partly saturated, hydrogenated PAO product, e.g., ata temperature from 25° C. to 350° C. (e.g., 100° C. to 300° C.), for atime period from 5 minutes to 100 h (e.g., from 5 minutes to 24 h), at ahydrogen pressure of from 25 psig to 2500 psig (˜170 kPag to ˜17 MPag),such as from 100 psig to 2000 psig (˜690 kPag to ˜14 MPag). Furtherinformation on hydrogenation of unsaturated PAO products can be found inU.S. Pat. No. 5,573,657 and “Lubricant Base Oil Hydrogen RefiningProcesses” (page 119 to 152 of Lubricant Base Oil and Wax Processing, byAvilino Sequeira, Jr., Marcel Dekker, Inc., NY, 1994).

This hydrogenation process can be accomplished, e.g., in a slurryreactor, in a batch operation, or in a continuous stirred tank reactor(CSTR), where the catalyst in 0.001 wt % to 20 wt % of the unsaturatedPAO feed (e.g., from 0.01 wt % to 10 wt %), hydrogen, and the uPAOs canbe continuously added to the reactor to allow for certain residencetime, e.g., 5 minutes to 10 h, to allow desired (e.g., substantiallycomplete) hydrogenation of the unsaturated olefins. The amount ofcatalyst added may usually be very small, just to compensate forcatalyst deactivation. The catalyst and hydrogenated PAO can becontinuously withdrawn from the reactor. The product mixture can befiltered, centrifuged, or settled to remove the solid hydrogenationcatalyst. The catalyst can be regenerated and reused, if desired. Thehydrogenated PAO can be used as-is or further distilled or fractionatedto a desired level. In some cases, when the hydrogenation catalyst showlittle or no catalyst deactivation over long term operation, the stirtank hydrogenation process can be carried out in a manner where a fixedamount of catalyst is maintained in the reactor, such as from 0.1 wt %to 10% of the total reactant, with mostly (or only) hydrogen and PAOfeed continuously added at certain feed rate, and with predominantly (oronly) hydrogenated PAO was withdrawn from the reactor.

The hydrogenation process can additionally or alternatively beaccomplished by a fixed bed process, in which the solid catalyst can bepacked inside a tubular reactor and heated to reactor temperature.Hydrogen and PAO feed can be fed through the reactor simultaneously fromthe top or bottom or counter-current, e.g., to maximize the contactbetween hydrogen, PAO, and catalyst and to allow superior heatmanagement. The feed rate of the PAO and hydrogen can be adjusted togive proper residence time, e.g., to allow desired (typicallysubstantially complete) hydrogenation of the unsaturated PAOs in thefeed. The hydrogenated PAO fluid can be used as-is or further distilledor fractionated to a desired level. Usually, the hydrogenated PAOproduct can have a bromine number of 2.0 or less.

IV.7 Functionalization

At least a portion of the unsaturated PAO product can be reacted with achemical reagent to obtain an at least partly functionalized PAOproduct. However, due to the individual nature of functionalizationreactions, the specificity of potential side products or by-products tobe avoided, the breadth of potentially desired functionality, and thusthe breadth of potential reaction conditions available or sufficient toattain desired functionality, it can be difficult to specify anappropriately set of conditions, reactors, chemical reagents, and/orcatalysts/additives/etc. to encompass them all. Nevertheless,conventional functionalization techniques, as well as their reactionparameters, are known to those skilled in the chemical arts, allowingpartially or completely functionalized PAO products sporting any one ormore of a variety of functional groups to be readily attainable. In thecase of substantially or completely functionalized PAO products, in someembodiments, the bromine number may be 2.0 or less.

V. Lubricant Base Stock

The unsaturated PAO products and the hydrogenated PAO products of thepresent invention, advantageously obtainable by using the processes ofthe present invention, can be used as a base stock for lubricating oilcompositions. Preferably the hydrogenated PAO product having a brominenumber no greater than 2.0 is used as a lubricating oil base stock. Thebase stock can be at any viscosity grade useful for any particularlubricating oil composition. The base stocks of the present inventioncan be blended with each other, other API Group I, II, III, IV, or Vbase stocks, lubricating additive packages, and/or the like, to form alubricating oil composition. “Lubricating oil,” “lubricating oilcomposition,” and “lubricant” are used herein interchangeably. Thelubricants can include internal combustion engine oils, gas turbineoils, automobile drive line fluids, power transfer fluids (e.g.,hydraulic oil), processing oils, heat transfer oils (e.g., transformeroils), industrial lubricants, gear box lubricants, and the like, as wellas combinations thereof.

VI. Additional Embodiments

Additionally or alternatively, the present invention can include one ormore of the following embodiments:

Embodiment 1. A process for making a poly alpha-olefin, PAO, the processcomprising:

contacting a feed comprising a C₆-C₃₂ alpha-olefin with a catalystsystem comprising a metallocene compound in a polymerization reactorunder polymerization conditions to effect a polymerization reaction toobtain a polymerization reaction mixture comprising vinylidenes,tri-substituted vinylenes, optionally di-substituted vinylenes, andoptionally vinyls; and

obtaining an unsaturated PAO product from the polymerization reactionmixture, wherein the unsaturated PAO product comprises vinylidenes,tri-substituted vinylenes, optionally di-substituted vinylenes,optionally vinyls, preferably wherein the conversion is 60% or more, and

wherein the metallocene compound is represented by formula (F-MC):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl orsilylcarbyl group;

R⁴ and R⁵ are each independently a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₃₀ hydrocarbyl or silylcarbyl group whereR⁴ and R⁵, taken together with the carbon atoms in the firstcyclopentadienyl ring to which they are directly connected, collectivelyform one or more substituted or unsubstituted rings annelated to thefirst cyclopentadienyl ring;

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl, silylcarbyl, or germanyl group, and optionally at leastthree of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are not hydrogen;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and m is an integer equal to v-2.

Embodiment 2. A process for making a poly alpha-olefin, PAO, the processcomprising: contacting a feed containing a C₆-C₃₂ alpha-olefin with acatalyst system comprising a metallocene compound in a polymerizationreactor under polymerization conditions to effect a polymerizationreaction to obtain a polymerization reaction mixture comprisingvinylidenes, tri-substituted vinylenes, and optionally di-substitutedvinylenes, and optionally vinyls; and obtaining an unsaturated PAOproduct from the polymerization reaction mixture, wherein thepolymerization reaction exhibits a selectivity toward greater than orequal to about 80 mol % vinylidenes, preferably 90 mol % vinylidenes,more preferably 96.5 mol % vinylidenes, based on total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes inthe unsaturated PAO product;

-   -   wherein the metallocene compound is represented by formula (I):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup, wherein a first one of R¹, R², and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; a second one of R¹, R², and R³ is hydrogen; and a third one ofR¹, R², and R³ is hydrogen, a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

R¹⁶ is a substituted or unsubstituted linear, branched linear, or cyclicC₁-C₂₀ hydrocarbyl group or silylcarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 3, 4, or 5 transition metal having an integer coordinationnumber of v, such as 3, 4, or 5; and

m is an integer equal to v-2, such as 1, 2 or 3.

Embodiment 3. The process according to embodiment 1 or 2, wherein R² ishydrogen.Embodiment 4. The process according to embodiment 1, 2, or 3 wherein oneof R¹ and R³ is a substituted or unsubstituted linear, branched linear,or cyclic C₁-C₆ hydrocarbyl group, and the other one of R¹ and R³ is ahydrogen.Embodiment 4.5. The process of embodiment 1, 2, 3, or 4, wherein theconversion is 10% (preferably 40%) or more and the polymerizationreaction exhibits a selectivity toward greater than or equal to about 80mol % vinylidenes, preferably 90 mol % vinylidenes, more preferably 96.5mol % vinylidenes, based on total moles of vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes in theunsaturated PAO product.Embodiment 4.6. The process of any of embodiments 1 to 4.5, wherein R²is hydrogen and one of R¹ and R³ is a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₆ hydrocarbyl group, and theother one of R¹ and R³ is a hydrogen.Embodiment 5. The process according to any one of embodiments 1 through4.6, wherein C₂ to C₅ alpha olefins are absent from the feed.Embodiment 6. The process according to any one of embodiments 1 through5 wherein: one of R¹ and R³ comprise an alpha Group 14 atom directlyattached to the indenyl ring, a beta Group 14 atom attached to the alphaatom, and two or more, preferably three, substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₈ hydrocarbyl groups attached tothe beta atom.Embodiment 7. The process according to any one of embodiments 1 through6, wherein the metallocene compound is represented by formula (II):

wherein:

R¹ and R² are hydrogen;

R²³ and R¹⁹ comprise Group 14 atoms, such as C, Si, or Ge;

R²⁰, R²¹, and R²² are independently hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup and at least two of R²⁰, R²¹, and R²² are independently asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group, wherein at least two of R²⁰, R²¹, and R²² are asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring;

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroup;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 4 transition metal having an integer coordination number ofv; and

m is an integer equal to v-2.

Embodiment 8. The process according to any one of Embodiments 1 through7, wherein R⁶ and R⁷, or R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together withthe respective carbon atoms in the indenyl ring to which they aredirectly connected, form a ring annelated to the indenyl ring.Embodiment 9. The process according to embodiment 8, wherein the ringannelated to the indenyl ring comprises one or more saturated carbonatoms.Embodiment 10. The process according to any one of embodiments 1 through9, wherein at least four of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are eachindependently a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₈ hydrocarbyl group, preferably methyl or ethyl.Embodiment 11. The process according to any one of embodiments 1 through10, wherein each R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₈hydrocarbyl group, preferably R¹⁶ is a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₈ hydrocarbyl group, preferablymethyl or ethyl.Embodiment 12. The process according to any one of embodiments 1 through11, wherein:

i) at least three of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ if present are nothydrogen;

ii) two or more of R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ if present together form afused ring or ring system;

iii) at least two of R⁶, R⁷, R¹⁷, and R¹⁸ are hydrogen;

iv) each X is independently a halogen or a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₆ hydrocarbyl group;

v) M comprises Zr or Hf;

or a combination thereof.

Embodiment 13. The process according to any one of embodiments 1 through12, wherein R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₈hydrocarbyl group, preferably methyl or ethyl.Embodiment 14. The process according to any one of embodiments 1 through13, wherein the metallocene compound is represented by formula (I-B),(III-B), (IV-B), (VI), (VIII), (IX), (X), (XI), (XII), (XV), (XVII),(XVIII), or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched linear,or cyclic hydrocarbyl group, or two or more X moieties may together forma fused ring or ring system; M is Hf or Zr; and m is 2.Embodiment 15. The process according to any one of embodiments 1 through14 wherein the metallocene is not represented by formula (I-B).Embodiment 16. The process according to any one of embodiments 1 through15, wherein the polymerization reaction exhibits a selectivity toward acombination of greater than or equal to about 96.5 mol % vinylidenes,from 0.5 mol % to 3.5 mol % tri-substituted vinylenes, less than orequal to about 1.5 mol % di-substituted vinylenes, and less than orequal to about 1.5 mol % vinyls, based on total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes inthe unsaturated PAO product.Embodiment 17. The process according to any one of embodiments 1 through16, wherein the polymerization reaction exhibits a selectivity toward acombination of vinylidenes of equal to or greater than 97.0 mol %,preferably equal to or greater than 97.9 mol %; tri-substitutedvinylenes of less than 2.1 mol %; di-substituted vinylenes of 0.5 mol %or less; and vinyls of 1.0 mol % or less, based on total moles ofvinyls, vinylidenes, di-substituted vinylenes, and tri-substitutedvinylenes in the unsaturated PAO product.Embodiment 18. The process according to any one of embodiments 1 through17, wherein the polymerization reaction exhibits a selectivity towards acombination of vinylidenes and tri-substituted vinylenes of collectivelygreater than 98.0 mol %, preferably greater than 98.5 mol %, and acombination of di-substituted vinylenes and vinyls of collectively lessthan 2.0 mol %, preferably less than 1.5 mol %, based on total moles ofvinyls, vinylidenes, di-substituted vinylenes, and tri-substitutedvinylenes in the unsaturated PAO product.Embodiment 19. The process according to any one of embodiments 1 through18, wherein the polymerization reaction results in the unsaturated PAOproduct having a number average molecular weight (Mn) of 1500 g/mol orless, preferably from 300 to 800 g/mol, as measured by ¹H NMR.Embodiment 20. The process according to any one of embodiments 1 through19, wherein the catalyst system further comprises a non-coordinatinganion type activator, preferably wherein the non-coordinating anion typeactivator comprises: N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate,

N,N-dimethylanilinium tetrakis(perfluoro-naphthyl)borate,

triphenylcarbonium tetrakis(perfluorophenyl)borate,

triphenylcarbonium tetrakis(perfluoronaphthyl)borate,

N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,

N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,

or combinations thereof.

Embodiment 21. The process according to any one of embodiments 1 through20, wherein:

the polymerization conditions comprise a reaction temperature from 40°C. to 150° C.;

an average activity level of at least 1200 g/s·mol;

the polymerization reaction mixture exhibits a yield of at least 10%;

or a combination thereof.

Embodiment 22. The process according to any one of embodiments 1 through21, further comprising:

a) contacting the unsaturated PAO product with hydrogen to convert atleast a portion of the unsaturated PAO product to a hydrogenated PAOproduct;

b) contacting the unsaturated PAO product with a chemical reagent toconvert at least a portion of the unsaturated PAO product to afunctionalized PAO product; or a combination thereof.

Embodiment 23. The process according to any one of embodiments 1 through22, wherein:

the feed comprises C₆-C₂₄ alpha-olefin;

wherein any combination of C₂-C₅ alpha-olefins are collectively presentin the alpha-olefin feed at no higher than 25 mol %, based on the totalmoles of the alpha-olefins supplied to the polymerization reactor,preferably wherein the alpha-olefin feed is substantially free ofethylene, propylene, C₄ alpha-olefins, and C₅ alpha-olefins;

or a combination thereof.

Embodiment 24. An unsaturated poly alpha-olefin (PAO) product producedaccording to any one of embodiments 1 through 23.Embodiment 25. An unsaturated poly alpha-olefin (PAO) product comprisinggreater than or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes contained therein and having an Mn of lessthan 5000 g/mol as determined by ¹H NMR.Embodiment 26. The unsaturated poly alpha-olefin (PAO) product ofembodiment 24 or embodiment 25, comprising:

96.5 mol % to 99.9 mol % of vinylidenes;

0.1 mol % to 3.5 mol % of ti-substituted vinylenes;

3.0 mol % or less of di-substituted vinylenes;

3.0 mol % or less of vinyl groups; based on total moles of vinylidenes,tri-substituted vinylenes, di-substituted vinylenes, and vinylidenescontained therein; and

a number average molecular weight (Mn) of 1500 g/mol or less as measuredby ¹H NMR.

Embodiment 27. The unsaturated poly alpha-olefin (PAO) product accordingto any one of embodiments 24 through 26, comprising:

less than or equal to about 1.0 mol % di-substituted vinylenes, whenpresent;

less than or equal to about 1.0 mol % vinyl groups when present; and

a number average molecular weight (Mn) of 1000 g/mol or less as measuredby ¹H NMR.

Embodiment 28. The unsaturated poly alpha-olefin (PAO) product accordingto any one of embodiments 24 through 27, comprising from 98 mol % to99.5 mol % of a combination of vinylidenes and tri-substitutedvinylenes; 0.5 mol % to 2 mol % of a combination of di-substitutedvinylenes and vinyl groups; and a number average molecular weight (Mn)of 800 g/mol or less as measured by ¹HNMR.Embodiment 29. A catalyst compound suitable to produce an unsaturatedPAO product according to any one of embodiments 24 through 28.Embodiment 30. A catalyst compound suitable to produce an unsaturatedPAO product from C₆-C₃₂ alpha-olefin under polymerization conditions,comprising:

a polymerization selectivity suitable to form an unsaturated PAO productcomprising:

greater than or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; represented bythe formula (F-MC2):

in which one of R¹, R², and R³ is an alpha Group 14 atom directlyattached to the indenyl ring, and a beta Group 14 atom attached to thealpha atom, and two or more, preferably three, substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroups attached to the beta atom, and either:

-   -   (i) two of R¹, R², and R³ are each hydrogen, or    -   (ii) one of R¹, R², and R³ is hydrogen and one of R¹, R², and        R³, taken together with R¹⁶ is a bridging group connecting the        first and second cyclopentadienyl rings;

R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently a hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₂₀ hydrocarbyl group or silylcarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

m is an integer equal to v-2.

Embodiment 31. The catalyst compound according to embodiments 29 or 30,wherein the polymerization selectivity is suitable to form anunsaturated PAO product comprising:

96.5 mol % to 99.9 mol % of vinylidenes;

0.1 mol % to 3.5 mol % of tri-substituted vinylenes;

2.0 mol % or less of di-substituted vinylenes;

2.0 mol % or less of vinyl groups;

based on total moles of vinyls, vinylidenes, di-substituted vinylenes,and tri-substituted vinylenes in the unsaturated PAO product; and

a number average molecular weight (Mn) of 1500 g/mol or less as measuredby ¹H NMR.

Embodiment 32. The catalyst compound according to any one of embodiments29 through 31, represented by formula (I), (II), (F-MC2), or (IV):

wherein:

i) according to formula (I):

a first one of R¹ or R³ is a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;

a second one of R¹, R², and R³ is a hydrogen;

the third one of R¹, R², and R³ is a hydrogen connecting the indenyl andcyclopentadienyl rings;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; and

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup or R¹⁶ may be a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₂₀, preferably C₁-C₈, hydrocarbyl groupsilylcarbyl group; or

ii) according to formula (II):

R¹ and R² are hydrogen;

R²³ and R¹⁹ comprise Group 14 atoms, such as C, Si, or Ge (preferablyR²³ is carbon and R¹⁹ is carbon or silicon);

R²⁰, R²¹, and R²² are independently hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup, wherein at least two of R²⁰, R²¹, and R²² are a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup, or two of R⁶, R⁷, R¹⁷, and R¹⁸ taken together with the carbonatoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring; and

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; or

iii) according to formula (F-MC2):

one of R¹ and R³ is a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₂₀ hydrocarbyl group;

two of R¹, R², and R³ are each hydrogen;

R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently hydrogen, asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₃₀hydrocarbyl group, or two of R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ taken togetherwith the carbon atoms in the benz-indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings annelated to the benz-indenyl ring; and

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; or

iv) according to formula (IV):

one of R¹ and R³ is a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₂₀ hydrocarbyl group;

two of R¹, R², and R³ are each hydrogen;

R⁶, R¹⁸, R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷ are each independently hydrogen, asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₃₀hydrocarbyl group, or two of R⁶, R¹⁸, R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷ takentogether with the carbon atoms in the cyclopentan-indenyl ring to whichthey are directly connected, collectively form one or more substitutedor unsubstituted rings annelated to the cyclopentan-indenyl ring; and

R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

wherein in the formulae (I), (II), (III), (IV):

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a transition metal having an integer coordination number of v; and

m is an integer equal to v-2.

Embodiment 33. The catalyst compound according to any one of embodiments29 through 32, comprising a polymerization selectivity suitable to forman unsaturated PAO product comprising:

greater than or equal to about 96.5 mol % vinylidenes;

less than or equal to about 3.5 mol % tri-substituted vinylenes;

less than or equal to about 1.0 mol % di-substituted vinylenes, whenpresent;

less than or equal to about 1.0 mol % vinyl groups when present; basedon total moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; and

a number average molecular weight (Mn) of 1500 g/mol or less as measuredby ¹H NMR.

Embodiment 34. The catalyst compound according to any one of embodiments29 through 33, represented by formula (III-B), (IV-B), (VI), (VIII),(IX), (X), (XI), (XII), (XV), (XVII), (XVIII), or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched linear,or cyclic hydrocarbyl group, or two or more X moieties may together forma fused ring or ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

m is an integer equal to v-2.

This invention further relates to:

1. A process for making a poly alpha-olefin, PAO, the processcomprising:

contacting a feed comprising a C₆-C₃₂ alpha-olefin with a catalystsystem comprising a metallocene compound in a polymerization reactorunder polymerization conditions to effect a polymerization reaction toobtain a polymerization reaction mixture comprising vinylidenes,tri-substituted vinylenes, optionally di-substituted vinylenes, andoptionally vinyls; and

obtaining an unsaturated PAO product from the polymerization reactionmixture, wherein the unsaturated PAO product comprises vinylidenes,tri-substituted vinylenes, optionally di-substituted vinylenes,optionally vinyls,

wherein the metallocene compound is represented by formula (F-MC):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl orsilylcarbyl group;

R⁴ and R⁵ are each independently a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₃₀ hydrocarbyl or silylcarbyl group whereR⁴ and R⁵, taken together with the carbon atoms in the firstcyclopentadienyl ring to which they are directly connected, collectivelyform one or more substituted or unsubstituted rings annelated to thefirst cyclopentadienyl ring;

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl, silylcarbyl, or germanyl group, and optionally at leastthree of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are not hydrogen;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to v-2.

2. The process of paragraph 1 wherein: the process comprises obtainingan unsaturated PAO product from the polymerization reaction mixture,wherein the polymerization reaction exhibits a selectivity towardgreater than or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; and

wherein the metallocene compound is represented by formula (I):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup, wherein a first one of R¹, R², and R³ is a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; a second one of R¹, R², and R³ is hydrogen; and a third one ofR¹, R², and R³ is hydrogen, a substituted or unsubstituted linear,branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup;

R¹⁶ is a substituted or unsubstituted linear, branched linear, or cyclicC₁-C₂₀ hydrocarbyl group or silylcarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

m is an integer equal to v-2.

3. The process of paragraph 1, wherein the conversion is 10% or more andthe polymerization reaction exhibits a selectivity toward greater thanor equal to about 80 mol % vinylidenes, preferably 90 mol % vinylidenes,more preferably 96.5 mol % vinylidenes, based on total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes inthe unsaturated PAO product.4. The process of paragraph 2, where in the conversion is 40% or more.5. The process of paragraph 1 or 2, wherein R² is hydrogen.6. The process of paragraph 1 or 2, wherein R² is hydrogen and at leastone of R¹ and R³ is not hydrogen.7. The process of paragraph 1 or 2, wherein R² is hydrogen and one of R¹and R³ is a substituted or unsubstituted linear, branched linear, orcyclic C₁-C₆ hydrocarbyl group, and the other one of R¹ and R³ is ahydrogen.8. The process of any paragraphs 1 to 7, wherein: one of R¹ and R³comprise an alpha Group 14 atom directly attached to the indenyl ring, abeta Group 14 atom attached to the alpha atom, and two or more,preferably three, substituted or unsubstituted linear, branched linear,or cyclic C₁-C₈ hydrocarbyl groups attached to the beta atom.9. The process of any paragraphs 1, 2, 3, or 4, wherein the metallocenecompound is represented by formula (II):

wherein:

R¹ and R² are hydrogen;

R²³ and R¹⁹ comprise Group 14 atoms, preferably C, Ge, or Si;

R²⁰, R²¹, and R²² are independently hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup and at least two of R²⁰, R²¹, and R²² are independently asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group, wherein at least two of R²⁰, R²¹, and R²² are asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring;

R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroup;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

m is an integer equal to v-2.

10. The process of any paragraphs 2 to 9 wherein R⁶ and R⁷, or R⁷ andR¹⁷, or R¹⁷ and R¹⁸, taken together with the respective carbon atoms inthe indenyl ring to which they are directly connected, form a ringannelated to the indenyl ring.11. The process of paragraph 10 wherein the ring annelated to theindenyl ring comprises one or more saturated carbon atoms.12. The process of any of paragraphs 1 to 11 wherein at least four ofR¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroup, preferably methyl or ethyl.13. The process of paragraph 12, wherein each R¹², R¹³, R¹⁴, R¹⁵, andR¹⁶ are independently a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₈ hydrocarbyl group, preferably R¹⁶ is asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₈hydrocarbyl group, preferably methyl or ethyl.14. The process of any of paragraphs 1 to 13 wherein:

i) at least three of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₈hydrocarbyl group;

ii) two or more of R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ if present together form afused ring or ring system;

iii) at least two of R⁶, R⁷, R¹⁷, and R¹⁸ are hydrogen;

iv) each X is independently a halogen or a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₆ hydrocarbyl group;

v) M comprises Zr or Hf;

or a combination thereof.15. The process of any of paragraphs 1 to 14, wherein R¹², R¹³, R¹⁴,R¹⁵, and R¹⁶ are each independently a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₈ hydrocarbyl group, preferablymethyl or ethyl.16. The process of any of paragraphs 1 to 15, wherein the metallocenecompound is represented by formula (I-B), (III-B), (IV-B), (VI), (VIII),(IX), (X), (XI), (XII), (XV), (XVII), (XVIII), or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched linear,or cyclic hydrocarbyl group, or two or more X moieties may together forma fused ring or ring system;

M is Hf or Zr; and m is 2.

17. The process of paragraph 16 wherein the metallocene is notrepresented by formula (I-B).18. The process of any of paragraphs 1 to 17, wherein the polymerizationreaction exhibits a selectivity toward a combination of greater than orequal to about 96.5 mol % vinylidenes, from 0.5 mol % to 3.5 mol %tri-substituted vinylenes, less than or equal to about 1.5 mol %di-substituted vinylenes, and less than or equal to about 1.5 mol %vinyls, based on total moles of vinyls, vinylidenes, di-substitutedvinylenes, and tri-substituted vinylenes in the unsaturated PAO product.19. The process of any of paragraphs 1 to 18, wherein the polymerizationreaction exhibits a selectivity toward a combination of vinylidenes ofequal to or greater than 97.0 mol %, preferably equal to or greater than97.9 mol %; tri-substituted vinylenes of less than 2.1 mol %;di-substituted vinylenes of 0.5 mol % or less; and vinyls of 1.0 mol %or less, based on total moles of vinyls, vinylidenes, di-substitutedvinylenes, and tri-substituted vinylenes in the unsaturated PAO product.20. The process of any of paragraphs 1 to 19, wherein the polymerizationreaction exhibits a selectivity towards a combination of vinylidenes andtri-substituted vinylenes of collectively greater than 98.0 mol %,preferably greater than 98.5 mol %, and a combination of di-substitutedvinylenes and vinyls of collectively less than 2.0 mol %, preferablyless than 1.5 mol %, based on total moles of vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes in theunsaturated PAO product.21. The process of paragraph 1, wherein the polymerization reactionresults in the unsaturated PAO product having a number average molecularweight (Mn) of 1500 g/mol or less, preferably from 300 to 800 g/mol, asmeasured by ¹H NMR.22. The process of any of paragraphs 1 to 21, wherein the catalystsystem further comprises a non-coordinating anion type activator,preferably wherein the non-coordinating anion type activator comprises:N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,triphenylcarbonium tetrakis(perfluorophenyl)borate,triphenylcarbonium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,or combinations thereof.23. The process of any of paragraphs 1 to 22, wherein: thepolymerization conditions comprise a reaction temperature from 40° C. to150° C.; an average activity level of at least 1200 g/s·mol; thepolymerization reaction mixture exhibits a yield of at least 10%; or acombination thereof.24. The process of any of paragraphs 1 to 23, further comprising:

a) contacting the unsaturated PAO product with hydrogen to convert atleast a portion of the unsaturated PAO product to a hydrogenated PAOproduct;

b) contacting the unsaturated PAO product with a chemical reagent toconvert at least a portion of the unsaturated PAO product to afunctionalized PAO product;

or a combination thereof.

25. The process of any of paragraphs 1 to 24, wherein any combination ofC₂-C₅ alpha-olefins are collectively present in the alpha-olefin feed atno higher than 25 mol %, based on the total moles of the alpha-olefinssupplied to the polymerization reactor, preferably wherein thealpha-olefin feed is substantially free of ethylene, propylene, C₄alpha-olefins, and C₅ alpha-olefins; or a combination thereof.26. An unsaturated poly alpha-olefin (PAO) product comprising greaterthan or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes contained therein and having an Mn of lessthan 5000 g/mol as determined by ¹H NMR.27. An unsaturated poly alpha-olefin (PAO) product comprising:

96.5 mol % to 99.9 mol % of vinylidenes;

0.1 mol % to 3.5 mol % of tri-substituted vinylenes;

3.0 mol % or less of di-substituted vinylenes;

3.0 mol % or less of vinyl groups; based on total moles of vinylidenes,tri-substituted vinylenes, di-substituted vinylenes, and vinylidenescontained therein; and

a number average molecular weight (Mn) of 1500 g/mol or less as measuredby ¹H NMR.

28. An unsaturated poly alpha-olefin (PAO) product comprising greaterthan or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes contained therein, and

less than or equal to about 1.0 mol % di-substituted vinylenes, whenpresent;

less than or equal to about 1.0 mol % vinyl groups when present; and

a number average molecular weight (Mn) of 1000 g/mol or less as measuredby ¹H NMR.

29. An unsaturated poly alpha-olefin (PAO) product comprising greaterthan or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes contained therein, and from 98 mol % to 99.5mol % of a combination of vinylidenes and tri-substituted vinylenes; 0.5mol % to 2 mol % of a combination of di-substituted vinylenes and vinylgroups, and a number average molecular weight (Mn) of 800 g/mol or lessas measured by ¹HNMR.30. A catalyst compound suitable to produce an unsaturated PAO productfrom C₆-C₃₂ alpha-olefin under polymerization conditions, comprising:

a polymerization selectivity suitable to form an unsaturated PAO productcomprising:

greater than or equal to about 80 mol % vinylidenes, preferably 90 mol %vinylidenes, more preferably 96.5 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; represented bythe formula (F-MC2):

in which one of R¹, R², and R³ is an alpha Group 14 atom directlyattached to the indenyl ring, and a beta Group 14 atom attached to thealpha atom, and two or more, preferably three, substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroups attached to the beta atom, and two of R¹, R², and R³ are eachhydrogen;

R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently a hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group;

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branchedlinear, or cyclic C₁-C₂₀ hydrocarbyl group or silylcarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

m is an integer equal to v-2.

31. The catalyst compound of paragraph 30, wherein the polymerizationselectivity is suitable to form an unsaturated PAO product comprising:

96.5 mol % to 99.9 mol % of vinylidenes;

0.1 mol % to 3.5 mol % of ti-substituted vinylenes;

2.0 mol % or less of di-substituted vinylenes;

2.0 mol % or less of vinyl groups;

based on total moles of vinyls, vinylidenes, di-substituted vinylenes,and tri-substituted vinylenes in the unsaturated PAO product; and

a number average molecular weight (Mn) of 1500 g/mol or less as measuredby ¹H NMR.

32. A catalyst compound represented by formula (I), (II), (F-MC2), or(IV):

wherein:

i) according to formula (I):

-   -   a first one of R¹ or R³ is a substituted or unsubstituted        linear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;    -   a second one of R¹, R², and R³ is a hydrogen;    -   the third one of R¹, R², and R³ is a hydrogen;    -   R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, a        substituted or unsubstituted linear, branched linear, or cyclic        C₁-C₃₀ hydrocarbyl group; and    -   R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted        or unsubstituted linear, branched linear, or cyclic C₁-C₂₀        hydrocarbyl group or silylcarbyl group or R¹⁶ may be a        substituted or unsubstituted linear, branched linear, or cyclic        C₁-C₂₀, preferably C₁-C₈, hydrocarbyl group or silylcarbyl        group; or    -   ii) according to formula (II):    -   R¹ and R² are hydrogen;    -   Q and R¹⁹ comprise Group 14 atoms, preferably C or Si        (preferably Q is carbon and R¹⁹ is carbon or silicon);    -   R²⁰, R²¹, and R²² are independently hydrogen or a substituted or        unsubstituted linear, branched linear, or cyclic C₁-C₂₀        hydrocarbyl group, wherein at least two of R²⁰, R²¹, and R²² are        a substituted or unsubstituted linear, branched linear, or        cyclic C₁-C₂₀ hydrocarbyl group;    -   R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, a        substituted or unsubstituted linear, branched linear, or cyclic        C₁-C₃₀ hydrocarbyl group, or two of R⁶, R⁷, R¹⁷, and R¹⁸ taken        together with the carbon atoms in the indenyl ring to which they        are directly connected, collectively form one or more        substituted or unsubstituted rings annelated to the indenyl        ring; and    -   R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted        or unsubstituted linear, branched linear, or cyclic C₁-C₂₀        hydrocarbyl group; or

iii) according to formula (F-MC2):

-   -   one of R¹ and R³ is a substituted or unsubstituted linear,        branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;    -   two of R¹, R², and R³ are each hydrogen;    -   R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently hydrogen, a        substituted or unsubstituted linear, branched linear, or cyclic        C₁-C₃₀ hydrocarbyl group, or two of R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹        taken together with the carbon atoms in the benz-indenyl ring to        which they are directly connected, collectively form one or more        substituted or unsubstituted rings annelated to the benz-indenyl        ring; and    -   R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently a substituted        or unsubstituted linear, branched linear, or cyclic C₁-C₂₀        hydrocarbyl group; or

iv) according to formula (IV):

-   -   one of R¹ and R³ is a substituted or unsubstituted linear,        branched linear, or cyclic C₁-C₂₀ hydrocarbyl group;    -   two of R¹, R², and R³ are each hydrogen;    -   R⁶, R¹⁸, R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷ are each independently        hydrogen, a substituted or unsubstituted linear, branched        linear, or cyclic C₁-C₃₀ hydrocarbyl group, or two of R⁶, R¹⁸,        R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷ taken together with the carbon atoms        in the cyclopentan-indenyl ring to which they are directly        connected, collectively form one or more substituted or        unsubstituted rings annelated to the cyclopentan-indenyl ring;        and    -   R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently a substituted        or unsubstituted linear, branched linear, or cyclic C₁-C₂₀        hydrocarbyl group;        wherein in the formulae (I), (II), (III), and (IV):

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or two or more X moieties together form a fused ringor ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and

m is an integer equal to v-2.

33. The catalyst compound according to paragraph 31, comprising apolymerization selectivity suitable to form an unsaturated PAO productcomprising:

greater than or equal to about 96.5 mol % vinylidenes;

less than or equal to about 3.5 mol % tri-substituted vinylenes;

less than or equal to about 1.0 mol % di-substituted vinylenes, whenpresent;

less than or equal to about 1.0 mol % vinyl groups when present; basedon total moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; and

a number average molecular weight (Mn) of 1500 g/mol or less as measuredby ¹H NMR.

34. The catalyst compound of paragraph 32, represented by formula(III-B), (IV-B), (VI), (VIII), (IX), (X), (XI), (XII), (XV), (XVII),(XVIII), or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched linear,or cyclic hydrocarbyl group, or two or more X moieties may together forma fused ring or ring system;

M is a group 3, 4 or 5 transition metal having an integer coordinationnumber of v; and m is an integer equal to v-2.

Examples

All reactions were done in a nitrogen purged box unless otherwisestated.

Synthesis of Pentamethyleyclopentadienyl(1-methylbenz[e]indenyl) HfMe₂(1A)

To a solution of CeCl₃ (12.2 g, 49.4 mmol) in THF (10 ml) was added 1.6MMeLi diethyl ether solution (31 ml, 49.4 mmol). The mixture was stirredat −35° C. for 30 minutes. Then2,3-dihydro-1H-cyclopenta[a]naphthalen-1-one (6.0 g, 32.9 mmol) in THF(20 ml) was added into the reaction mixture. The color of the reactionmixture changed from yellow to black after stirring for 3 hr. Thereaction mixture was allowed to stir at room temperature for 16 h. Thereaction was taken out of the nitrogen purged box and quenched with 5 mlof saturated NH₄Cl aqueous solution (stirred for 10 min). The solidswere precipitated with water and the top clear solution was decantedinto a clean beaker. The solids were washed with Et₂O. The organicphases were combined and dried with MgSO₄. Solvents were then removedunder vacuum. The crude product was isolated as a dark oil which wasdissolved into 50 ml of CH₂Cl₂. To the reaction mixture was addedcatalytic amount of p-toluenesulfonic acid (50 mg). The reaction wasstirred at room temperature for 30 min. then washed with saturatedNaHCO₃ (aq) followed by saturated brine. The organic phase was separatedand dried over MgSO₄. Solvents were removed and the crude product waspurified by column flash chromatograph. Product was eluted out by 10%CH₂Cl₂ in hexane. Solvents were then removed and 1-methylbenz[e]indenewas isolated as white solid (2.7 g).

To the solution of 1-methylbenz[e]indene (2.7 g, 15 mmol) in Et₂O (30ml) was slowly added 11M nBu Li (1.37 ml, 15 mmol). The reaction wasstirred at room temperature for 30 min. The lithiated product was slowlycrushed out as a white solid. 20 ml of hexane was added, then filteredto collect the product as a white solid (2.7 g). The lithiated product(1.4 g, 7.5 mmol) was mixed with CpMe₅HfCl₃ (3.15 g, 7.5 mmol) in Et₂O(15 ml) and stirred overnight. Et₂O was then removed by a stream ofnitrogen and the crude product was reslurried into hexane for 15 min.The product was isolated by filtration as a mixture of LiCl and was usedfor the next step with no further purification.

The crude hafnocene dichloride (4.4 g, 7 mmol) was slurried into toluene(30 ml) and MeMgI (4.9 ml, 3 M in Et₂O) was then added and the reactionwas stirred at 70° C. for 16 h. The reaction was cooled to roomtemperature and 1,4-dioxane (2 ml) was added. The mixture was stirredfor 15 min and solids were removed by filtration on CELITE and waswashed by Et₂O. Volatiles were then removed under vacuo. Final product(C₂₆H₃₂Hf) was isolated as a solid (3.35 g), which was analyzed by ¹HNMR (CD₂Cl₂, 400 MHz): δ 8.28 (d, J=8.2 Hz, 1H), 7.70 (dd, J=7.9, 1.6Hz, 1H), 7.46 (dd, J=8.3, 7.1 Hz, 1H), 7.41-7.30 (m, 2H), 7.00 (d, J=9.0Hz, 1H), 5.43 (d, J=2.8 Hz, 1H), 5.34 (d, J=2.9 Hz, 1H), 2.45 (s, 3H),1.82 (s, 15H), −1.19 (s, 3H), −2.23 (s, 3H).

Synthesis of Pentamethyleyclopentadienyl(3-methylbenz[e]indenyl) HfMe₂(B)

To a solution of a mixture of 1-methylbenz[e]indenyl Lithium and3-methylbenz[e]indenyl Lithium (0.46 g, 2.5 mmol, ratio=3:2) in Et₂O (15ml) was added CpMe₅HfCl₃ (1.05 g, 2.5 mmol). Then it was stirred at roomtemperature for 16 h. Solids were filtered off and washed by Et₂O. Thesolid that was filtered off was shown to be 90% 1-methylbenz[e]indenylCpMe₅HfCl₂ by NMR. Thereafter, Et₂O solution was collected and removed.The Crude product was isolated as a white solid and NMR showed that itcontained 90% 3-methylbenz[e]indenyl CpMe₅HfCl₂ and 10%1-methylbenz[e]indenyl CpMe₅HfCl₂. This product was reslurried back intoa small amount of Et₂O and stirred at 40° C. for 20 min. The solutionwas slowly cooled back to RT, then to −35° C. and left at −35° C. for 30min. The solution was then filtered to collect pure3-methylbenz[e]indenyl CpMe₅HfCl₂ (0.35 g, 0.69 mmol), which was thenslurried into toluene (5 ml), MeMgI (0.46 ml, 3 M in Et₂O) was added,and the reaction was stirred at 70° C. for 16 h. The reaction was cooledto room temperature and 1, 4-dioxane was added. The mixture was stirredfor 15 min and solids were removed by filtration on CELITE and werewashed by Et₂O. Volatiles were then removed under vacuum. The crudeproduct was reslurried into small amount of hexane. Final product(C₂₆H₃₂Hf) was isolated by filtration as a solid (0.13 g), which wasanalyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.79 (d, J=7.7, 1H), 7.69 (d,J=7.9, 1H), 7.58-7.48 (m, 2H), 7.43 (dt, J=22.1, 7.2, 2H), 5.91 (d,J=3.0 Hz, 1H), 5.46 (d, J=2.9 Hz, 1H), 2.25 (s, 3H), 1.89 (s, 15H),−1.04 (s, 3H), −2.43 (s, 3H).

1:1 Mixtures of Pentamethylcyclopentadienyl(1-methylbenz[e]indenyl)HfMe₂ and Pentamethylcyclopentadienyl(3-methylbenz[e]indenyl) HfMe₂(1A/B=1/1)

The compound was obtained by mixing two pure isomers in 1:1 ratio.

Synthesis of Tetramethylcyclopentadienyl(1-methylbenz[e]indenyl) HfMe₂(J)

To a solution of 1-methylbenz[e]indenyl Lithium (0.5 g, 2.7 mmol) in inEt₂O (15 ml) was added CpHMe₄ HfCl₃ (1.09 g, 2.7 mmol). The solution wasstirred overnight at room temperature. The dichloride product (1.34 g,2.3 mmol) was collected by filtration and was washed by Et₂O. It wasthen slurried into toluene (15 ml). MeMgI (1.5 ml, 3 M in Et₂O) wasadded and the reaction was stirred at 70° C. for 16 h. The reaction wascooled to room temperature and 1,4-dioxane was added. The mixture wasstirred for 15 min and solids were removed by filtration on CELITE andwas washed by Et₂O. Volatiles were then removed under vacuum. The crudeproduct was reslurried into small amount of toluene, heated to 70° C. todissolve the solids, then slowly cooled down to −35° C., and left at−35° C. for 3 h. Pure product recrystallized out of toluene. Finalproduct (C₂₅H₃₀Hf) was isolated by filtration as a solid (0.83 g), whichwas analyzed by 1H NMR (CD₂Cl₂, 400 MHz): δ 8.35 (d, J=8.2 Hz, 1H),7.81-7.76 (m, 1H), 7.55 (dd, J=8.3, 7.1, 1H), 7.49-7.38 (m, 2H), 7.17(d, J=9.0 Hz, 1H), 5.74-5.66 (m, 2H), 5.28 (s, 1H), 2.62 (s, 3H), 1.91(s, 3H), 1.90 (s, 3H), 1.86 (s, 3H), 1.80 (s, 3H), −1.09 (s, 3H), −1.90(s, 3H).

Synthesis of Pentamethyleyclopentadienyl(benz[e]indenyl) HfMe₂ (E)

To a solution of benz[e]indene (8.78 g, 52 mmol) in Et₂O (20 ml) wasslowly added 11M nBu Li (4.74 ml, 52 mmol). The reaction was stirred atroom temperature for 30 min. Lithiated product slowly precipitated outas a white solid. 20 ml of hexane was added, then filtered to collectthe product as a white solid (8.7 g). The lithiated product (0.38 g,2.19 mmol) and CpMe₅HfCl₃ (0.92 g, 2.19 mmol) were mixed in Et₂O (30 ml)and stirred overnight. The crude product (1.04 g) was isolated byfiltration as a mixture with LiCl and was used for the next step with nofurther purification. The crude hafnocene dichloride (1.04 g, 1.5 mmol)was slurried into toluene (10 ml), MeMgI (1.2 ml, 3 M in Et₂O) was thenadded, and the reaction was stirred at 70° C. for 16 h. The reaction wascooled to room temperature and 1,4-dioxane was added. The mixture wasstirred for 15 min and solids were removed by filtration on CELITE andwas washed by Et₂O. Volatiles were then removed under vacuum. Finalproduct (C₂₇H₃₆Hf) was isolated as a pale yellow solid (0.85 g), whichwas analyzed by 1H NMR (CD₂Cl₂, 400 MHz): δ 7.97 (dd, J=8.0, 1.4, 1H),7.83-7.76 (m, 1H), 7.57-7.34 (m, 4H), 6.46 (ddd, J=3.1, 2.1, 0.9 Hz,1H), 6.03 (dd, J=3.2, 2.0 Hz, 1H), 5.71 (t, J=3.2 Hz, 1H), 1.90 (s,15H), −1.52 (s, 3H), −1.69 (s, 3H).

Synthesis of Dimethylsilyl tetramethyleyclopentadienyl(3-benz[e]indenyl)HfMe₂ (K)

To a solution of AgOTf (0.6 g, 2 mmol) in toluene (5 ml) was addedMe₂SiClCpMe₄H (0.5 g, 2 mmol). The reaction was stirred for 10 min, andthe solids were removed by filtration. The toluene was then removedunder vacuum. The product (0.71 g) was isolated as a clear oil and wasused for the next step with no further purification. The triflatederivative (0.71 g, 2 mmol) was mixed with benz[e]indenyl lithium (0.37g, 2 mmol) in Et₂O (15 ml) and stirred for 20 min. After the Et₂O wasremoved under vacuo, the crude product was reslurried into hexane andthen filtered through a pad of silica gel. The silica gel was washed byhexane followed by 5 ml of Et₂O. All solvents were removed under vacuum.Product was isolated as a yellow oil, which was used with no furtherpurification. The yellow oil (0.68 g, 2 mmol) was dissolved into 10 mlof Et₂O and 11 M nBu Li (0.37 ml, 4 mmol) was slowly added while thereaction stored at room temperature for 20 min. After addition of 20 mlof hexane, the lithiated product was slowly precipitated out as a whitesolid which was collected by filtration. The lithiated product (0.78 g,2 mmol) and HfCl₄ (0.53 g, 2 mmol) were then mixed in Et₂O (15 ml) andstirred for 2 h. The crude product was collected by filtration andwashed by Et₂O. The crude product was slurried into dichloromethane (10ml) and filtered to collect pure product as a yellow solid.Dichloromethane was used to extract the crude product twice. Aftersolvent was removed, 0.25 g dichloride product isolated, which wasslurried into toluene (10 ml). MeMgI (0.28 ml, 3 M in Et₂O) was thenadded and the reaction was stirred at 80° C. for 16 h. The reaction wascooled to room temperature and 1, 4-dioxane was added. The mixture wasstirred for 15 min and solids were removed by filtration on CELITE andwas washed by Et₂O. Volatiles were then removed under vacuum. Finalproduct (C₂₆H₃₂HfSi) was isolated as a pale yellow solid (0.2 g), whichwas analyzed by 1H NMR (CD₂Cl₂, 400 MHz): δ 8.24 (d, J=7.8 Hz, 1H), 7.81(dd, J=7.9, 1.4 Hz, 1H), 7.63-7.58 (m, 2H), 7.50 (ddd, J=8.3, 7.1, 1.3Hz, 1H), 7.36 (s, 2H), 5.82 (d, J=3.2 Hz, 1H), 1.98 (s, 3H), 1.95 (s,3H), 1.87 (s, 3H), 1.84 (s, 3H), 1.00 (s, 3H), 0.81 (s, 3H), −0.73 (s,3H), −2.20 (s, 3H).

Synthesis of n-Butylcyclopentadienyl(1-methylbenz[e]indenyl) ZrMe₂ (L)

To a solution of 1-methylbenz[e]indenyl Lithium (0.26 g, 1.4 mmol) inEt₂O (15 ml) was added n-Butylcyclopentadienyl ZrCl₃ (0.46 g, 1.4 mmol).The solution was stirred overnight at room temperature. All solventswere then removed under vacuum. The solids were then slurried in a smallamount of toluene. The mixture was heated to 70° C. to allow the solidsto dissolve, then slowly cooled to −35° C. and allowed to stand at −35°C. for 2 h. Product (0.35 g) was collected by filtration. Thezirconocene dichloride (0.35 g, 0.7 mmol) was slurried into toluene (5ml), MeMgI (0.46 ml, 3 M in Et₂O) was then added, and the reaction wasstirred at 70° C. for 16 h. The reaction was cooled to room temperatureand sufficient 1,4-dioxane was added. The mixture was stirred for 15 minand solids were removed by filtration on CELITE and was washed by Et₂O.Volatiles were then removed under vacuum. Final product (C₂₅H₃₀Zr) wasisolated as an oil (0.18 g), which was analyzed by ¹H NMR (CD₂Cl₂, 400MHz): δ 8.33 (d, J=8.2, 1H), 7.78 (dd, J=7.9, 1.5 Hz, 1H), 7.56 (ddd,J=8.3, 7.1, 1.5 Hz, 1H), 7.46 (ddd, J=7.9, 7.1, 1.3 Hz, 1H), 7.36 (d,J=9.0 Hz, 1H), 7.24 (d, J=9.0 Hz, 1H), 6.09 (q, J=3.2 Hz, 2H), 5.79-5.64(m, 2H), 5.57 (td, J=2.9, 2.2 Hz, 2H), 2.69 (s, 3H), 2.29 (dd, J=8.5,6.9 Hz, 2H), 1.53-1.40 (m, 2H), 1.38-1.23 (m, 2H), 0.89 (t, J=7.3 Hz,3H), −0.70 (s, 3H), −1.17 (s, 3H).

Synthesis of Pentamethyleyclopentadienyl(1-propylbenz[e]indenyl) HfMe₂(C)

To a solution of mixture of 1-propylbenz[e]indenyl Lithium and3-propylbenz[e]indenyl Lithium (0.59 g, 2.75 mmol, ratio=2:1) in Et₂O(20 ml) was added CpMe5HfCl3 (1.16 g, 2.75 mmol). Then it was stirred atroom temperature for 16 h. The solids were filtered off and washed byEt₂O. After removal of solvent, the crude product was slurried in hexane(15 ml) and stirred for 30 min. The solid product was collected byfiltration and was reslurried into Et₂O (30 ml). The solution was heatedto 40° C. and cooled to room temperature. The solid product wascollected by filtration. ¹HNMR study showed that the ratio of two isomerwas 1:0.07. The solids were then reslurried into 2.5 ml toluene andheated to 70° C. to dissolve the solids, then slowly cooled to −35° C.,and allowed to stand −35° C. for 16 h. Pure product (0.3 g) was isolatedby filtration. The pure hafnocene dichloride (0.3 g, 0.56 mmol) wasslurried into toluene (10 ml), MeMgI (0.37 ml, 3 M in Et₂O) was thenadded, and the reaction was stirred at 70° C. for 16 h. The reaction wascooled to room temperature and 1,4-dioxane (1 ml) was added. The mixturewas stirred for 15 min and solids were removed by filtration on CELITEand was washed by Et₂O. Volatiles were then removed under vacuum. Finalproduct (C₂₈H₃₆Hf) was isolated as a solid (0.29 g), which was analyzedby ¹H NMR (C₆D₆, 500 MHz): δ 8.49 (d, J=8.2 Hz, 1H), 7.66 (d, J=7.8 Hz,1H), 7.46-7.36 (m, 2H), 7.27 (dd, J=8.0, 7.0 Hz, 1H), 6.97 (d, J=9.0 Hz,1H), 5.32 (d, J=2.8 Hz, 1H), 5.25 (d, J=2.9 Hz, 1H), 3.34 (ddd, J=14.6,9.6, 4.8 Hz, 1H), 2.55 (ddd, J=14.6, 9.7, 6.8 Hz, 1H), 1.83-1.71 (m,16H), 1.66-1.48 (m, 1H), 0.95 (t, J=7.3 Hz, 3H), −0.62 (s, 3H), −1.70(s, 3H).

Synthesis of Pentamethyleyclopentadienyl(3-neopentylbenz[e]indenyl)HfMe₂ (2)

Benz[e]indenyl lithium (0.50 g, 3 mmol) was mixed with neopentylOMs(0.48 g, 3 mmol) in THF (15 ml) and stirred at 75° C. for 2 days. THFwas removed under vacuo and the crude product was reslurried intopentane. The solids were removed by filtration. Then the crude productwas eluted on silica gel by 5% DCM in hexane. Relatively pure productwas obtained as a clear oil (0.36 g, 2 mmol). To the solution of theclear oil (0.36 g, 2 mmol) in Et₂O (20 ml) was slowly added 11M nBu Li(0.15 ml) and the reaction was stirred at room temperature for 30 min.Et₂O was removed by a stream of nitrogen. The crude lithiated productwas reslurried into 1 ml cold pentane, then pentane was immediatelypipetted out. Any solvent residue was removed by vacuum. The product(0.33 g, 1 mml) was mixed with CpMe₅HfCl₃ (0.57 g, 1 mmol) in Et₂O (15ml) and was stirred overnight. LiCl was removed by filtration. Half ofEt₂O was then removed under vacuo and pentane was added. 3-substitutedhafnium dichloride (0.15 g, 0.24 mmol) was collected by filtration. Thedichloride was reslurried into toluene (15 ml). MeMgI (0.16 ml, 3 M inEt₂O) was added and the reaction was stirred at 75° C. for 48 h. Thereaction was cooled to room temperature and 1,4-dioxane was added. Themixture was stirred for 15 min and solids were removed by filtration onCELITE and was washed by Et₂O. Volatiles were then removed under vacuo.The product (C₃₀NH₄₀Hf) slowly solidifies at −35° C., which was analyzedby ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.83-7.78 (m, 1H), 7.74-7.70 (m, 1H),7.59 (d, J=0.8 Hz, 1H), 7.51-7.40 (m, 4H), 5.98 (d, J=2.9, 1H), 5.47 (d,J=2.9 Hz, 1H), 2.89 (d, J=14.1 Hz, 1H), 2.26 (s, 1H), 1.90 (s, 15H),0.95 (s, 9H), −1.02 (s, 3H), −2.41 (s, 3H).

Synthesis of Pentamethyleyclopentadienyl(1-methylindenyl) HfMe₂ (4)

1-Methylindenyl lithium (0.421 g, 2 mmol) was mixed with CpMe5HfCl3(0.65 g, 2 mmol) in Et₂O (15 ml) and stirred for 2.5 h. The product wasisolated by filtration as a mixture of LiCl and was washed by smallamount of Et₂O. It was used for the next step without furtherpurification. The crude hafnium dichloride (0.53 g, 0.95 mmol) wasslurried into toluene (20 ml). MeMgI (0.64 ml, 3 M in Et2O) was addedand the reaction was stirred at 70° C. for 16 h. The reaction was cooledto room temperature and 1,4-dioxane (0.4 ml) was added. The mixture wasstirred for 15 min and solids were removed by filtration on CELITE andwas washed by Et₂O. Volatiles were then removed under vacuo. Finalproduct (C₂₂H₃₀Hf) was isolated as a solid (0.4 g), which was analyzedby ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.66-7.52 (m, 1H), 7.26-7.07 (m, 3H),5.45 (dd, J=2.9, 0.8 Hz, 1H), 5.40 (dd, J=2.9, 0.6 Hz, 1H), 2.23 (s,3H), 1.89 (s, 15H), −1.05 (s, 3H), −2.10 (s, 3H).

Pentamethyleyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)HfMe₂(3) Synthesis

1-Methyl (1,5,6,7-tetrahydro-s-indacenyl) lithium (0.3 g, 1.6 mmol) wasmixed with CpMe₅HfCl₃ (0.7 g, 1.1 mmol) in Et₂O (15 ml) and stir itovernight. Et₂O was then removed by a stream of nitrogen and the crudeproduct was reslurried into pentane for 15 min and was cooled under −35°C. The product was isolated by filtration as a mixture of LiCl and wasused for the next step with no further purification. The crude hafniumdichloride (0.78 g, 1.4 mmol) was slurried into toluene (20 ml) andMeMgI (0.94 ml, 3 M in Et₂O) was then added and the reaction was stirredat 70° C. for 16 h. The reaction was cooled to room temperature and1,4-dioxane was added. The mixture was stirred for 15 min, and thesolids were removed by filtration on CELITE and washed by Et₂O.Volatiles were then removed under vacuo. Final product (C₂₅H₃₄Hf) wasisolated as a solid (0.4 g), which was analyzed by ¹H NMR (CD₂Cl₂, 400MHz): δ 7.45-7.33 (m, 1H), 7.02-6.92 (m, 1H), 5.32 (dd, J=2.9, 0.9 Hz,1H), 5.27 (dd, J=2.8, 0.6 Hz, 1H), 2.99-2.86 (m, 4H), 2.19 (s, 3H),2.11-1.99 (m, 2H), 1.88 (s, 15H), −1.08 (s, 3H), −2.12 (s, 3H).

Synthesis ofPentamethyleyclopentadienyl(1-1,5,6,7-tetrahydro-s-indacenyl)HfMe₂ (5)

1,5,6,7-tetrahydro-s-Indacenyl lithium (0.15 g, 0.9 mmol) was mixed withCpMe₅HfCl₃ (0.39 g, 0.9 mmol) in Et₂O (15 ml) and stirred overnight.Et₂O was then removed by a stream of nitrogen and the crude product wasreslurried into hexane for 15 min. The product was isolated byfiltration as a mixture of LiCl and was used for the next step with nofurther purification. The crude hafnium dichloride (0.46 g, 0.8 mmol)was slurried into toluene (20 ml), MeMgI (0.57 ml, 3 M in Et₂O) wasadded and the reaction stirred at 70° C. for 16 h. The reaction wascooled to room temperature and 1,4-dioxane (0.4 ml) was added. Themixture was stirred for 15 min and solids were removed by filtration onCELITE and washed by Et₂O. Volatiles were then removed under vacuo.Final product (C₂₄H₃₂Hf) was isolated as a solid (0.38 g), which wasanalyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.25 (s, 2H), 5.81 (d, J=3.2 Hz,2H), 5.55 (t, J=3.2 Hz, 1H), 2.94 (t, J=7.3 Hz, 4H), 2.06 (p, J=7.3 Hz,2H), 1.89 (s, 15H), −1.49 (s, 6H).

Pentamethyleyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)ZrMe₂ (6) Synthesis

1-Methyl (1,5,6,7-tetrahydro-s-indacenyl) lithium (0.2 g, 1.1 mmol) wasmixed with CpMe₅ZrCl₃ (0.37 g, 1.1 mmol) in Et₂O (15 ml) and stir itovernight. Et₂O was then removed by a stream of nitrogen and the crudeproduct was reslurried into pentane for 15 min. The product was isolatedby filtration as a mixture of LiCl and was used for the next step withno further purification.

The crude zirconium dichloride (0.34 g, 0.73 mmol) was slurried intotoluene (20 ml), MeMgI (0.48 ml, 3 M in Et2O) was then added, and thereaction was stirred at 70° C. for 16 h. The reaction was cooled to roomtemperature and 1,4-dioxane (0.4 ml) was added. The mixture was stirredfor 15 min and solids were removed by filtration on CELITE and waswashed by Et₂O. Volatiles were then removed under vacuo. Final product(C₂₅H₃₄Zr) was isolated as a solid (0.3 g), which was analyzed by ¹H NMR(CD₂Cl₂, 400 MHz): δ 7.39 (s, 1H), 7.01-6.95 (m, 1H), 5.30 (dd, J=2.9,0.8 Hz, 1H), 5.26 (dd, J=2.9, 0.6 Hz, 1H), 3.00-2.82 (m, 4H), 2.22 (d,J=0.5 Hz, 3H), 2.04 (p, J=7.4 Hz, 2H), 1.83 (s, 15H), −0.91 (s, 3H),−1.96 (s, 3H).

Synthesis ofPentamethylcyclopentadienyl(1-trimethylsilylmethylbenz[e]indenyl) HfMe₂(16) andPentamethylcyclopentadienyl(3-trimethylsilylmethylbenz[e]indenyl) HfMe₂(7)

Benz[e]indenyl lithium (0.3 g, 1.7 mmol) was mixed with TMSCH₂OTf (0.41g, 1.7 mmol) in THF (8 ml) and stirred at room temperature overnight.THF was removed under vacuo, and the crude product was reslurried intopentane. Solids were removed by filtration. Solvents were removed by astream of nitrogen. The crude product was isolated as a red oil with aratio of 1:0.9 1-substituted vs 3-substituted. To the solution of thered oil (0.42 g, 1.7 mmol) in Et₂O (20 ml) was slowly added 11 M nBuLi(1.04 ml). The reaction was stirred at room temperature for 30 min. Et₂Owas removed by a stream of nitrogen. The lithiated product was collectedas a solid and was used with no further purification. The lithiatedproduct (0.4 g, 2 mmol) was mixed with CpMe₅HfCl₃ (0.65 g, 2 mmol) inEt₂O (15 ml) and stirred for 3 h. The precipitated solid was collectedby filtration. The crude Et₂O was saved for 1-substituted productseparation. NMR showed that it was the pure 3-substituted product (0.4g, 0.6 mmol), which was slurried into toluene (6 ml). MeMgI (0.4 ml, 3 Min Et₂O) was then added and the reaction was stirred at 70° C. for 16 h.The reaction was cooled to room temperature and 1,4-dioxane (0.2 ml) wasadded. The mixture was stirred for 15 min and solids were removed byfiltration on CELITE and washed by Et₂O. Volatiles were then removedunder vacuo. Purepentamethylcyclopentadienyl(3-trimethylsilylmethylbenz[e]indenyl)hafnium(IV) dimethyl was isolated as a solid (0.32 g), which wasanalyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.80-7.75 (m, 1H), 7.71-7.63 (m,1H), 7.50-7.30 (m, 4H), 5.87 (d, J=2.9, 1H), 5.27 (d, J=2.8 Hz, 1H),2.41 (d, J=14.4 Hz, 1H), 1.88 (s, 15H), 1.55 (d, J=14.4 Hz, 1H), −0.02(s, 9H), −1.03 (s, 3H), −2.45 (s, 3H).

The crude Et₂O solution was allowed to sit at RT for 1 day. Pure1-substituted product (0.17 g, 0.27 mmol) was slowly crystalized out,and slurried into toluene (6 ml). MeMgI (0.18 ml, 3 M in Et₂O) was thenadded and the reaction was stirred at 70° C. for 16 h. The reaction wascooled to room temperature and 1,4-dioxane (0.1 ml) was added. Themixture was stirred for 15 min and solids were removed by filtration onCELITE and washed by Et₂O. Volatiles were then removed under vacuo. Purepentamethylcyclopentadienyl(1-trimethylsilylmethylbenz[e]indenyl)hafnium(IV) dimethyl was isolated as a solid (0.12 g), which wasanalyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 8.42-8.32 (m, 1H), 7.74 (dd,J=7.8, 1.5 Hz, 1H), 7.50 (ddd, J=8.3, 7.1, 1.5 Hz, 1H), 7.45-7.35 (m,2H), 7.04 (d, J=9.0 Hz, 1H), 5.47 (d, J=2.8 Hz, 1H), 5.23 (d, J=2.8 Hz,1H), 2.90 (d, J=14.7 Hz, 1H), 1.89 (s, 15H), 1.76 (d, J=14.8 Hz, 1H),−0.06 (s, 9H), −1.04 (s, 3H), −2.22 (s, 3H).

Pentamethylcyclopentadienyl (1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)HfMe₂ synthesis (8)

1-isoButyl-1,5,6,7-tetrahydro-s-indacenyl lithium (0.27 g, 1.2 mmol) wasmixed with CpMe₅HfCl₃ (0.52 g, 1.2 mmol) in Et₂O (20 ml) and stirredovernight. Et₂O was then removed by a stream of nitrogen and the crudeproduct was reslurried into pentane for 15 min. The mixture was cooledat −35° C. for 1 h. The product was isolated by filtration as a mixtureof LiCl and was used for the next step with no further purification. Thecrude hafnium dichloride (0.68 g, 1.1 mmol) was slurried into toluene(20 ml) and MeMgI (0.71 ml, 3 M in Et₂O) was then added and the reactionwas stirred at 70° C. for 16 h. The reaction was cooled to roomtemperature and 1,4-dioxane (0.38 ml) was added. The mixture was stirredfor 15 min and solids were removed by filtration on CELITE and washed byEt₂O. Volatiles were then removed under vacuo. The product slowly becamea solid, to which was added 0.5 ml of pentane. This was swirled andcooled at −35° C. for 3 h, and pentane was pipetted away. Final product(C₂₅H₄₀Hf) was isolated as a solid (0.4 g), which was analyzed by ¹H NMR(CD₂Cl₂, 400 MHz): δ 7.38 (s, 1H), 6.97 (d, J=1.4 Hz, 1H), 5.34 (dd,J=2.9, 0.8 Hz, 1H), 5.27 (d, J=2.9 Hz, 1H), 2.99-2.88 (m, 4H), 2.80 (dd,J=13.5, 5.8 Hz, 1H), 2.04 (p, J=7.3 Hz, 2H), 1.93-1.79 (m, 17H), 0.93(d, J=6.5 Hz, 3H), 0.85 (d, J=6.4 Hz, 3H), −1.08 (s, 2H), −2.14 (s, 3H).

Synthesis of (neopentyl-indenyl) (pentamethyl-cyclopentadienyl) HfMe₂(9)

To a precooled, stirring suspension of(pentamethyl-cyclopentadienyl)hafnium trichloride (0.298 g, 0.709 mmol)in toluene (5 mL), lithium neopentyl-indenide (0.140 g, 0.719 mmol, 1.01eq) was added with toluene (5 mL). The reaction was stirred at roomtemperature for 22 h. The reaction was filtered over CELITE. Thefiltered solid was further extracted with dichloromethane. Thedichloromethane and toluene extracts were combined and concentratedunder a stream of nitrogen and then under high vacuum to give a paleyellow solid. The solid was stirred in hexane (10 mL) and then filtered.The filtered solid was washed with additional hexane (5 mL). The solidwas collected and concentrated under high vacuum to afford the productas an off-white solid (0.296 g, 73%). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.60(dq, 1H, J=8.4, 1.1 Hz), 7.30 (dt, 1H, J=8.5, 1.1 Hz), 7.24-7.12 (m,2H), 6.03 (d, 1H, J=2.9 Hz), 5.86 (dd, 1H, J=2.9, 0.8 Hz), 2.99 (d, 1H,J=14.3 Hz), 2.15 (d, 1H, J=14.3 Hz), 2.06 (s, 15H), 0.87 (s, 9H).

To a stirring suspension of (neopentyl-indenyl)(pentamethyl-cyclopentadienyl) hafnium chloride (0.282 g, 0.495 mmol),in toluene (20 mL), methylmagnesium bromide (3.0 M in diethyl ether,0.33 mL, 0.99 mmol, 2.0 eq) was added. The reaction was heated to 65° C.for 19 h. Then, additional methylmagnesium bromide (3.0 M in diethylether, 0.2 mL, 1.2 eq) was added. The reaction was stirred and heated to65° C. for Id. The reaction was concentrated under a stream of nitrogenwhile still hot from the reaction. The reaction was further concentratedunder high vacuum. The residue was extracted with hexane (10 mL, then 5mL) and filtered over CELITE. The combined hexane extracts wereconcentrated under a stream of nitrogen and then under high vacuum togive an oil, which eventually formed a white solid (0.178 g, 68%). ¹HNMR (400 MHz, C₆D₆): δ 7.64 (dq, 1H, J=8.5, 1.0 Hz), 7.16-7.14 (m, 2H),7.11-7.06 (m, 1H), 5.35-5.31 (m, 2H), 3.02 (d, 1H, J=14.1 Hz), 2.06 (d,1H, J=14.1 Hz), 1.76 (s, 15H), 0.95 (s, 9H), −0.58 (s, 3H), −1.57 (s,3H).

Synthesis of (pentamethyl-cyclopentadienyl)((trimethylsilyl)-methyl-1,5,6,7-tetrahydro-s-indacenyl) HfMe₂ (10)

To a stirring suspension of (pentamethyl-cyclopentadienyl) hafniumtrichloride (0.284 g, 0.676 mmol) in toluene (10 mL), lithium(trimethylsilyl)methyl-1,5,6,7-tetrahydro-s-indacenide (0.170 g, 0.684mmol, 1.01 eq) was added with toluene (5 mL). The reaction was stirredat room temperature for 5 h. The reaction was filtered over CELITE. Thefiltered solid was further extracted with dichloromethane (2×10 mL). Thedichloromethane and toluene extracts were combined and concentratedunder a stream of nitrogen and then under high vacuum to give a yellowoil. The oil was stirred in hexane (5 mL), causing a solid toprecipitate. The solid was allowed to settle, and the supernatant wasdiscarded. The solid was further washed with hexane (5 mL) andconcentrated under high vacuum to afford the product as an off-whitesolid (0.309 g, 73%). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.25 (d, 1H, J=1.8Hz), 7.04 (d, 1H, J=1.1 Hz), 5.67 (dd, 1H, J=2.8, 0.8 Hz), 5.63 (d, 1H,J=2.8 Hz), 3.06-2.85 (m, 4H), 2.52 (d, 1H, J=14.5 Hz), 2.14-1.95 (m,2H), 2.03 (s, 15H), 1.78 (d, 1H, J=14.5 Hz), −0.08 (s, 9H).

To a stirring solution of (pentamethyl-cyclopentadienyl)((trimethylsilyl)-methyl-1,5,6,7-tetrahydro-s-indacenyl) hafniumdichloride (0.309 g, 0.494 mmol) in toluene (20 mL), methylmagnesiumbromide (3.0 M in diethyl ether, 0.45 mL, 1.35 mmol, 2.74 eq) was added.The reaction was stirred and heated to 65° C. for 17 h. The reaction wasthen heated to 80° C. for Id. Additional methylmagnesium bromide (3.0 Min diethyl ether, 0.45 mL, 1.35 mmol, 2.74 eq) was added, and thereaction was stirred and heated at 80° C. for 16 h. The reaction wasconcentrated under a stream of nitrogen while still hot from thereaction. The reaction was further concentrated under high vacuum. Theresidue was extracted with hexane (2×20 mL) and filtered over CELITE.The combined hexane extracts were concentrated under a stream ofnitrogen and then under high vacuum to afford the product as anoff-white solid (0.208 g, 72%). ¹H NMR (400 MHz, C₆D₆): δ 7.43 (s, 1H),6.99 (d, 1H, J=1.0 Hz), 5.25 (dd, 1H, J=2.8, 0.7 Hz), 5.14 (d, 1H, J=2.8Hz), 2.99-2.71 (m, 4H), 2.56 (d, 1H, J=14.5 Hz), 1.98-1.72 (m, 2H), 1.80(s, 15H), 1.68 (d, 1H, J=14.5 Hz), 0.02 (s, 9H), −0.50 (s, 3H), −1.57(s, 3H).

Synthesis of (Neopentyl-1,5,6,7-tetrahydro-s-indacenyl)(pentamethyl-cyclopentadienyl) HfMe₂ (11)

To a stirring solution of lithiumneopentyl-1,5,6,7-tetrahydro-s-indacenide (0.251 g, 1.08 mmol, 1.01 eq)in toluene (5 mL), (pentamethyl-cyclopentadienyl) hafnium trichloride(0.450 g, 1.07 mmol) was added with toluene (10 mL). The reaction wasstirred at room temperature for Id. The reaction was filtered overCELITE. The filtered solid was further extracted with toluene (10 mL)and dichloromethane (10 mL). The dichloromethane and toluene extractswere combined and concentrated under a stream of nitrogen and then underhigh vacuum at 30° C. to give a pale yellow solid. The solid was washedwith hexane (2×5 mL) and concentrated under high vacuum to afford theproduct as an off-white powder (0.360 g, 55%). ¹H NMR (400 MHz, CD₂Cl₂):δ 7.38 (d, 1H, J=0.8 Hz), 7.07 (d, 1H, J=0.9 Hz), 5.88 (d, 1H, J=2.8Hz), 5.75 (dd, 1H, J=2.8, 0.8 Hz), 3.08-2.85 (m, 5H), 2.16-2.95 (m, 3H),2.04 (s, 15H), 0.86 (s, 9H).

To a stirring solution of (neopentyl-1,5,6,7-tetrahydro-s-indacenyl)(pentamethyl-cyclopentadienyl) hafnium dichloride (0.360 g, 0.590 mmol)in toluene (20 mL), methylmagnesium bromide (3.0 M in diethyl ether) wasadded. The reaction was stirred and heated to 80° C. for 2.5 d. Thereaction was concentrated under a stream of nitrogen while still hotfrom the reaction. The reaction was further concentrated under highvacuum. The residue was extracted with hexane (2×20 mL) and filteredover CELITE. The combined hexane extracts were concentrated under astream of nitrogen and then under high vacuum to afford the productcontaining hexane (0.14 eq) and toluene (0.05 eq) (0.358 g, 103%). ¹HNMR (400 MHz, C₆D₆): δ 7.57 (s, 1H), 7.01 (d, 1H, J=1.2 Hz), 5.31 (dd,1H, J=2.8, 0.8 Hz), 5.29 (d, 1H, J=2.9 Hz), 3.07 (d, 1H, J=14.0 Hz),2.99-2.74 (m, 4H), 2.07 (d, 1H, J=14.2 Hz), 1.99-1.81 (m, 2H), 1.79 (s,15H), 1.00 (s, 9H), −0.53 (s, 3H), −1.57 (s, 3H).

Synthesis of pentamethyleyclopentadienyl(1-methylindenyl) ZrMe₂ (12)

Pentamethylcyclopentadienyl(1-methylindenyl) ZrMe₂ (12) was synthesizedin an analogous fashion of 4 using Me₅CpZrCl₃.

Synthesis ofpentamethyleyclopentadienyl(1-1,5,6,7-tetrahydro-s-indacenyl) ZrMe₂ (13)

1,5,6,7-tetrahydro-s-Indacenyl lithium (0.15 g, 0.9 mmol) was mixed withCpMe₅ZrCl₃ (0.31 g, 0.9 mmol) in Et₂O (15 ml) and stirred overnight.Et₂O was then removed by a stream of nitrogen and the crude product wasreslurried into hexane for 15 min. The product was isolated byfiltration as a mixture of LiCl and was used for the next step with nofurther purification. The crude zirconocene dichloride (0.34 g, 0.7mmol) was slurried into toluene (20 ml). MeMgI (0.46 ml, 3 M in Et₂O)was then added and the reaction was stirred at 70° C. for 16 h. Thereaction was cooled to room temperature and 1,4-dioxane (0.4 ml) wasadded. The mixture was stirred for 15 min and solids were removed byfiltration on CELITE and washed by Et₂O. Volatiles were then removedunder vacuo. Final product (C₂₄H₃₂Zr) was isolated as a solid (0.26 g),which was analyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.27 (s, 2H), 5.86 (d,J=3.2 Hz, 2H), 5.54 (t, J=3.3 Hz, 1H), 2.92 (t, J=7.4 Hz, 4H), 2.06 (p,J=7.3 Hz, 2H), 1.85 (s, 15H), −1.32 (s, 6H).

Synthesis of Pentamethyleyclopentadienyl(2,7-di-tert-butylfluorenyl)HfMe₂ (14)

2,7-di-tert-Butylfluorenyl lithium (0.22 g, 0.7 mmol) was mixed withCpMe₅HfCl₃ (0.28 g, 0.7 mmol) in Et₂O (15 ml) and stir it overnight.Half of Et₂O was then removed by a stream of nitrogen and the crudeproduct was reslurried into pentane for 15 min. The product was isolatedby filtration as a mixture of LiCl and was used for the next step withno further purification.

The crude hafnocene dichloride (0.35 g, 0.5 mmol) was slurried intotoluene (20 ml). MeMgI (0.33 ml, 3 M in Et₂O) was then added and thereaction was stirred at 70° C. for 16 h. The reaction was cooled to roomtemperature and 1,4-dioxane (0.4 ml) was added. The mixture was stirredfor 15 min and solids were removed by filtration on CELITE and washed byEt₂O. Volatiles were then removed under vacuo. The crude product wasdissolved into pentane. Impure solids were removed by filtration onCELITE. Then pentane was removed. The product was isolated as a yellowsolid. Final product (C₃₃H₄₆Hf) was isolated as a solid (0.26 g), whichwas analyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.96 (d, J=8.8 Hz, 2H), 7.52(dd, J=8.8, 1.7 Hz, 2H), 7.21 (dd, J=1.8, 0.8 Hz, 2H), 5.52 (s, 1H),1.88 (s, 15H), 1.33 (s, 18H), −2.03 (s, 6H).

Pentamethyleyclopentadienyl(1-isoButyl-1,5,6,7-tetrahydro-s-indacenyl)ZrMe₂(15) synthesis

1-isoButyl-1,5,6,7-tetrahydro-s-indacenyl lithium (0.27 g, 1.2 mmol) wasmixed with CpMe₅ZrCl₃ (0.41 g, 1.2 mmol) in Et₂O (20 ml) and stirredovernight. Et₂O was then removed by a stream of nitrogen. The crudeproduct was reslurried into pentane for 15 min and cooled at −35° C. for1 h. The product was isolated by filtration as a mixture of LiCl and wasused for the next step with no further purification.

The crude zirconecene dichloride (0.55 g, 1 mmol) was slurried intotoluene (20 ml). MeMgI (0.67 ml, 3 M in Et₂O) was added and the reactionwas stirred at 70° C. for 16 h. The reaction was cooled to roomtemperature and 1,4-dioxane (0.35 ml) was added. The mixture was stirredfor 15 min and solids were removed by filtration on CELITE and washed byEt₂O. Volatiles were then removed under vacuo. The crude product was adark red oil, to which was added 0.5 ml of pentane. This was swirled andallowed to sit at −35° C. for 3 h. Pentane was pipetted away. Finalproduct (C₂₈H₄₀Zr) was isolated as colorless crystals (0.3 g), which wasanalyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.41 (s, 1H), 7.00 (d, J=1.4 Hz,1H), 5.34 (d, J=2.9, 1H), 5.26 (d, J=2.9 Hz, 1H), 3.04-2.73 (m, 5H),2.14-1.95 (m, 3H), 1.90-1.80 (m, 16H), 0.96 (d, J=6.6 Hz, 3H), 0.88 (d,J=6.5 Hz, 3H), −0.89 (s, 3H), −1.95 (s, 3H).

Synthesis of (Neopentyl-1,5,6,7-tetrahydro-s-indacenyl)(pentamethyl-cyclopentadienyl) ZrMe₂ (17)

To a stirring suspension of lithiumneopentyl-1,5,6,7-tetrahydro-s-indacenide (0.304 g, 1.309 mmol 1.01 eq)in toluene (30 mL), (pentamethyl-cyclopentadienyl) zirconium trichloride(0.433 g, 1.301 mmol) was added with toluene (20 mL). The reaction wasstirred at room temperature for 1 d. The reaction was filtered overCELITE. The filtered solid was further extracted with toluene (10 mL)and dichloromethane (10 mL). The dichloromethane and toluene extractswere combined and concentrated under a stream of nitrogen and then underhigh vacuum at 30° C. to give a yellow, crystalline solid (0.556 g,81%). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.41 (d, 1H, J=0.9 Hz), 7.09 (d, 1H,J=1.2 Hz), 5.87-5.85 (m, 2H), 3.03-2.84 (m, 5H), 2.17-1.92 (m, 3H), 1.98(s, 15H), 0.87 (s, 9H).

To a stirring solution of (neopentyl-1,5,6,7-tetrahydro-s-indacenyl)(pentamethyl-cyclopentadienyl) zirconium dichloride (0.556, 1.064 mmol)in toluene (10 mL), MeMgBr (3.0 M in diethyl ether) was added. Thereaction was stirred and heated to 80° C. for 2.5 d. The reaction wasconcentrated under a stream of nitrogen while still hot from thereaction. The reaction was further concentrated under high vacuum. Theresidue was extracted with hexane (2×10 mL) and filtered over CELITE.The combined hexane extracts were concentrated under a stream ofnitrogen and then under high vacuum to afford the product as a whitefoam (0.440 g, 85%). ¹H NMR (400 MHz, C₆D₆): δ 7.58 (d, 1H, J=1.2 Hz),7.02 (d, 1H, J=1.3 Hz), 5.30 (dd, 1H, J=2.9, 0.7 Hz), 5.26 (d, 1H, J=2.9Hz), 3.11 (d, 1H, J=14.1 Hz), 2.97-2.73 (m, 4H), 2.14 (d, 1H, J=14.1Hz), 1.99-1.79 (m, 2H), 1.75 (s, 15H), 1.01 (s, 9H), −0.36 (s, 3H),−1.40 (s, 3H).

Synthesis of(Pentamethylcyclopentadienyl)(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalenyl)Hafnium(IV)dimethyl (18)

Mix3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalenylLithium (0.24 g, 1 mmol) with CpMe₅HfCl₃ (0.41 g, 1 mmol) in Et₂O (10ml) and stir it overnight. Filter off all LiCl. All Et₂O was thenremoved by a stream of nitrogen and the crude product was used for thenext step with no further purification. The crude Hafnium dichloride(0.68 g, 1 mmol) was slurried into toluene (15 ml) and MeMgI (0.63 ml, 3M in Et₂O) was then added and the reaction was stirred at 70° C. for 16hours. The reaction was cooled to room temperature and 1, 4 dioxane wasadded. The mixture was stirred for 15 min and solids were removed byfiltration on celite and was washed by Et₂O. All volatiles were thenremoved under vacuo. The crude product was dissolved into minimum amountof pentane. Let it stay under −35° C. for 2 hr. Pipet out all pentanesolution. Final product (C₃₀H₄₄Hf) was isolated as a solid (0.30 g),which was analyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.51 (s, 1H), 7.13 (s,1H), 5.29 (q, J=2.8, Hz, 2H), 2.20 (s, 3H), 1.87 (s, 15H), 1.39 (s, 3H),1.28 (s, 3H), 1.261 (s, 3H), 1.256 (s, 3H), −1.09 (s, 3H), −2.14 (s,3H).

Synthesis ofPentamethylcyclopentadienyl(2,2,7-trimethyl-1,2,3,5-tetrahydro-s-indacenyl)Hafnium(IV)dimethyl (19)

Mix 2,2,7-trimethyl-1,2,3,5-tetrahydro-s-indacenyl Lithium (0.17 g, 0.8mmol) with CpMe₅HfCl₃ (0.34 g, 0.8 mmol) in Et₂O (20 ml) and stir itovernight. All Et₂O was then removed by a stream of nitrogen and thecrude product was reslurried into pentane for 15 min. The product wasisolated by filtration as a mixture of LiCl and was used for the nextstep with no further purification. The crude Hafnium dichloride (0.36 g,0.6 mmol) was slurried into toluene (15 ml) and MeMgI (0.38 ml, 3 M inEt₂O) was then added and the reaction was stirred at 70° C. for 16hours. The reaction was cooled to room temperature and 1, 4 dioxane wasadded. The mixture was stirred for 15 min and solids were removed byfiltration on celite and was washed by Et₂O. All volatiles were thenremoved under vacuo. Final product (C₂₇H₃₈Hf) was isolated as a solid(0.29 g), which was analyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ 7.32 (s,1H), 6.93 (d, J=1.1 Hz, 1H), 5.25 (d, J=2.8 Hz, 2H), 2.76 (d, J=1.5 Hz,2H), 2.72 (dd, J=4.7, 1.5 Hz, 2H), 2.18 (s, 3H), 1.87 (s, 15H), 1.15 (s,3H), 1.13 (s, 3H), −1.07 (s, 3H), −2.05 (s Hz, 3H).

Polymerization Examples

Solvents, polymerization grade toluene and/or isohexanes were suppliedby ExxonMobil Chemical Co. and were purified by passing through a seriesof columns: two 500 cc Oxyclear cylinders in series from Labclear(Oakland, Calif.), followed by two 500 cc columns in series packed withdried 3 A molecular sieves (8-12 mesh; Aldrich Chemical Company), andtwo 500 cc columns in series packed with dried 5 A molecular sieves(8-12 mesh; Aldrich Chemical Company).

1-decene monomer is purchased from Sigma Aldrich and is purified bypassing through a basic alumina column and dried over 3A molecularsieves before use. N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate (BF20) and N,N-dimethylaniliniumtetrakisperfluoronaphthylborate were purchased from AlbemarleCorporation. All complexes and the activators were added to the reactoras dilute solutions in toluene. The concentrations of the solutions ofactivator, scavenger, and complexes that were added to the reactor werechosen so that between 40-200 microliters of the solution were added tothe reactor to ensure accurate delivery.

Reactor Description and Preparation. Polymerizations were conducted inan inert atmosphere (N2) drybox using autoclaves equipped with anexternal heater for temperature control, glass inserts (internal volumeof reactor=23.5 mL), septum inlets, regulated supply of nitrogen, andequipped with disposable polyether ether ketone mechanical stirrers (800RPM). The autoclaves were prepared by purging with dry nitrogen at 110°C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

Typical decene polymerizations: The reactor was prepared as describedabove. Isohexane (enough to bring the total solution volume to 5.0 ml),and 1-decene (2.0 ml) were added via syringe at room temperature andatmospheric pressure. The reactor was then brought to processtemperature (60° C., 85° C., or 110° C.). Next, the stirrers where setto 800 RPM and the cells were pressurized to 80 PSI with N2. Scavengersolution (e.g., tri-n-octylaluminum, TNOA) was then added via syringe tothe reactor at process conditions. Activator (e.g., BF20) solution wasadded via syringe to the reactor at process conditions, followed by thepre-catalyst (i.e., MC) solution via syringe to the reactor at processconditions. Reactor temperature was monitored and typically maintainedwithin +/−1° C. Polymerizations were halted by addition of approximately50 psi 02/Ar (5 mole % O2) gas mixture to the autoclaves forapproximately 30 seconds. The polymerizations were quenched after 60minutes polymerization time. The reactors were cooled and vented. Thefinal PAO was isolated after the solvent, unreacted monomers, and othervolatiles were removed in-vacuo. Yields reported include total weight ofthe non-volatile PAO and residual catalyst. Catalyst activity isreported as grams of PAO per mol transition metal compound per second ofreaction time (a/s·mol) and is based on the weight of the isolated PAO.

Characterization of Isolated PAO

The reaction mixture was flashed under vacuum to remove the residualsolvent, unreacted monomer and volatile compounds to leave anunsaturated PAO product which is weighed to determine the isolatedyield. The unsaturated PAO product was analyzed (as follows) todetermine the distributions of vinylidenes (“Vd”), di-substitutedvinylenes (“Di”), tri-substituted vinylenes (“Tri”), and vinyls (“Vi”),the catalyst activity level, and physical properties such as numberaverage molecular weight. Conversion percentages of the reactions werecalculated from the isolated yield of products and the amount ofalpha-olefin used in the reaction. Specifically, conversion=gramsisolated PAO/grams alpha-olefin used (when reported in %,conversion=(grams isolated PAO/grams alpha-olefin used)×100).

Proton NMR (¹H-NMR) was used to determine the number average molecularweight of the unsaturated PAO and the quantitative breakdown of theolefinic structure types (e.g., vinyl, vinylene, di-substitutedvinylene, tri-substituted vinylene, and vinylidene).

Specifically, an NMR instrument of 500 MHz is run under the followingconditions: a ˜30° flip angle RF pulse, 128 scans, with a relaxationdelay of −5 s between pulses; sample (60-100 mg) dissolved in CDCl₃(deuterated chloroform) in a 5 mm NMR tube; and signal collectiontemperature at ˜25° C. The following approach is taken in determiningthe concentrations of the various olefins among all of the olefins froman NMR spectrum. First, peaks corresponding to different types ofhydrogen atoms in vinyls (T1), vinylidenes (T2), di-substitutedvinylenes (T3), and tri-substituted vinylenes (T4) are identified at thepeak regions in TABLE A below. Second, areas of each of the above peaks(A1, A2, A3, and A4, respectively) are then integrated. Third,quantities of each type of olefins (Q1, Q2, Q3, and Q4, respectively) inmoles are calculated (as A1/2, A2/2, A3/2, and A4, respectively).Fourth, the total quantity of all olefins (Qt) in moles is calculated asthe sum total of all four types (Qt=Q1+Q2+Q3+Q4). Finally, the molarconcentrations (C1, C2, C3, and C4, respectively, in mol %) of each typeof olefin, on the basis of the total molar quantity of all of theolefins, is then calculated (in each case, Ci=100*Qi/Qt).

TABLE A Hydrogen Atoms Peak Number of Concentration Type Olefin RegionPeak Hydrogen Quantity of of Olefin No. Structure (ppm) Area AtomsOlefin (mol) (mol %) T1 CH₂═CH-R¹ 4.95-5.10 A1 2 Q1 = A1/2 C1 T2CH₂═CR¹R² 4.65-4.84 A2 2 Q2 = A2/2 C2 T3 CHR¹═CHR² 5.31-5.55 A3 2 Q3 =A3/2 C3 T4 CR¹R²═CH R³ 5.11-5.30 A4 1 Q4 = A4  C4 The number averagemolecular weight was determined by: Mn = Saturated/(vinylene +vinylidene + vinyl + trisubstituted × 2) × 14 + 27 (“Saturated”,“vinylene”, “vinyl”, “trisubstituted” in this equation refer to peakarea integration)

1-Decene Polymerizations using N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate Activator

TABLE I below shows inventive Examples and Comparative Examples 1-36,listing reaction conditions including identity of the metallocenecompound (MC), the polymerization temperature, the yield of isolatedPAO, the catalyst activity, together with Mn, as measured by ¹H NMR, andthe distributions of the olefins in terms of mole percentages of eachtype, on the basis of the total moles of the four categories of olefinsas determined by ¹HNMR. Conversion=grams isolated PAO/grams alpha-olefinused (if reported in %, conversion=(grams isolated PAO/gramsalpha-olefin used)×100.

Samples having the same catalyst system was repeated at threepolymerization temperatures (60° C., 85° C., and 110° C.), with eachsample being tested twice at each temperature. The data in TABLE I showsthat polymerization using certain inventive metallocene compoundsresulted in extraordinarily high selectivity toward vinylidenes (Vd) ortoward a combination of vinylidenes and tri-substituted vinylenes (Tri),and in general, a very low selectivity toward di-substituted vinylenes(Di) and toward vinyl (Vi) groups. As such, the uPAO product mixturesfrom those inventive metallocene compounds may be particularly useful asintermediates for making hydrogenated and/or functionalized PAOmaterials, where the reactivity of vinylidenes and/ort-substitutedvinylenes are particularly high (and therefore desired).

TABLE I Catalyst 0.08 μmol (0.4 mmol/l in toluene), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (BF20) activator(0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Conditions Mn* % Mn*Temp Activity Olefins Distribution (%) Yield (g/ Conv. Vinylidene (avg)Ex. # MC (° C.) (g/s · mol) Di Vi Tri Vd (g) mol) %** (avg) (g/mol) 1 a1A 60 1370 0.7 3.6 2.6 93.1 0.394 1166 26.6 93.5 1153 b 60 1420 0.5 3.42.3 93.8 0.409 1140 27.6 2 a 1A 85 2320 0.3 3.3 2.6 93.7 0.669 555 45.193.8 538 b 85 2050 0.4 3.1 2.7 93.8 0.589 520 39.7 3 a 1A 110 2810 0.21.0 2.9 96.0 0.809 371 54.6 95.9 372 b 110 2810 0.2 1.2 2.8 95.8 0.809372 54.6 4 a B 60 721 0.3 4.5 3.8 91.4 0.208 1282 14.0 91.4 1285 b 60745 0.0 4.6 4.1 91.3 0.215 1287 14.5 5 a B 85 1460 0.3 5.1 4.3 90.30.421 632 28.4 89.8 636 b 85 1470 0.4 5.5 4.8 89.3 0.424 640 28.6 6 a B110 2170 0.2 3.3 5.3 91.2 0.625 413 42.2 91.2 415 b 110 2250 0.2 3.4 5.491.1 0.649 417 43.8 7 a 1A/ 60 1090 0.5 3.8 2.8 92.9 0.314 1203 21.292.6 1191 B (1:1) b 60 1100 0.7 3.8 3.2 92.3 0.318 1178 21.5 8 a 1A/ 851940 0.7 4.3 4.3 90.6 0.558 572 37.7 91.4 581 B (1:1) b 85 1900 0.4 4.23.3 92.1 0.547 589 36.9 9 a 1A/ 110 2280 0.3 3.1 4.0 92.6 0.658 402 44.493.1 405 B (1:1) b 110 2680 0.2 2.5 3.8 93.5 0.772 408 52.1 10 a C 60555 — 2.7 2.5 94.7 0.160 967 10.8 94.5 982 b 60 651 — 3.1 2.7 94.2 0.188996 12.7 11 a C 85 1440 — 3.9 3.4 92.8 0.416 535 28.1 93.5 541 b 85 1220— 3.1 2.7 94.2 0.351 546 23.7 12 a C 110 2980 — 1.6 3.0 95.5 0.860 36158.0 95.5 361 b 110 3290 — 1.4 3.2 95.4 0.947 361 63.9 13 a D 60 38200.9 23.0 3.4 72.6 1.10 3004 74.2 72.9 3039 b 60 3830 0.9 22.9 3.0 73.21.10 3074 74.2 14 a D 85 4340 1.2 12.0 4.3 82.5 1.25 987 84.3 83.3 1012b 85 4360 0.5 12.2 3.2 84.1 1.26 1036 85.0 15 a D 110 4130 0.5 5.9 3.490.2 1.19 578 80.3 90.0 577 b 110 4140 0.5 6.5 3.2 89.8 1.19 576 80.3 16a E 60 4240 3.7 6.4 3.8 86.1 1.22 4550 82.3 85.3 4445 b 60 4270 3.9 6.15.5 84.5 1.23 4339 83.0 17 a E 85 4540 2.3 2.1 6.8 88.8 1.31 1285 88.488.8 1288 b 85 4600 2.3 1.9 7.1 88.7 1.32 1291 89.1 18 a E 110 4050 1.44.1 6.1 88.4 1.17 729 78.9 87.7 723 b 110 4050 1.8 4.3 7.0 86.9 1.17 71778.9 19 a F^(c) 60 4370 3.3 — 7.3 89.4 1.26 1048 85.0 89.2 1044 b 604350 3.4 — 7.5 89.0 1.25 1040 84.3 20 a F^(c) 85 4380 4.1 — 11.6 84.31.26 551 85.0 84.3 551 b 85 4450 4.1 — 11.6 84.2 1.28 550 86.4 21 aF^(c) 110 4230 5.7 — 16.5 77.8 1.22 402 82.3 77.8 409 b 110 4240 5.6 —16.8 77.7 1.22 415 82.3 22 a G^(c) 60 1600 0.8 6.0 9.8 83.3 0.462 351931.2 83.4 3612 b 60 1540 0.9 6.0 9.8 83.4 0.443 3704 29.9 23 a G^(c) 852120 1.2 8.3 12.9 77.5 0.610 1311 41.2 78.9 1321 b 85 1990 0.5 7.6 11.680.2 0.572 1330 38.6 24 a G^(c) 110 1740 1.0 8.7 15.8 74.6 0.502 70233.9 74.9 702 b 110 1520 0.9 8.6 15.4 75.1 0.438 701 29.6 25 a H^(c) 602480 — 33.4 19.4 47.2 0.713 6554 48.1 49.2 6863 b 60 2590 — 33.4 15.451.2 0.745 7172 50.3 26 a H^(c) 85 3050 0.7 37.5 17.2 44.6 0.880 216759.4 44.6 2212 b 85 2600 0.9 37.4 17.2 44.5 0.748 2256 50.5 27 a H^(c)110 1660 0.7 30.8 17.6 50.9 0.478 953 32.3 51.3 892 b 110 2280 0.9 28.618.9 51.7 0.658 830 44.4 28 a J 60 1730 1.2 1.6 12.3 84.9 0.499 238633.7 84.3 2372 b 60 1740 1.4 1.9 12.9 83.7 0.502 2358 33.9 29 a J 852730 1.4 2.1 16.8 79.7 0.787 867 53.1 79.9 878 b 85 2870 1.3 2.0 16.680.0 0.826 888 55.7 30 a J 110 2910 1.4 1.6 20.8 76.2 0.838 509 56.576.3 511 b 110 2890 1.3 1.5 20.9 76.3 0.832 513 56.1 31 a K^(c) 60 412012.3  0.0 16.0 71.6 1.19 12368 80.3 67.6 12286 b 60 3970 15.9  0.0 20.663.5 1.14 12203 76.9 32 a K^(c) 85 4570 5.5 4.3 18.2 72.1 1.32 4740 89.172.0 4902 b 85 4610 5.5 4.4 18.2 71.9 1.33 5064 89.7 33 a K^(c) 110 38304.3 11.3 17.3 67.1 1.10 3020 74.2 66.5 3007 b 110 3710 4.4 11.4 18.465.8 1.07 2993 72.2 34 a L 60 485 9.6 — 12.5 77.9 0.140 1930 9.4 78.21959 b 60 486 9.8 — 11.8 78.4 0.140 1988 9.4 35 a L 85 815 8.1 0.4 12.179.4 0.235 864 15.9 79.1 863 b 85 887 8.3 0.6 12.4 78.7 0.256 861 17.336 a L 110 1330 8.9 0.4 14.2 76.5 0.383 534 25.8 75.8 525 b 110 1310 9.40.5 15.0 75.1 0.377 515 25.4 *Mn estimated by ¹H NMR; **Conv. %calculated from isolated yield and it is the minimum conversion due tovolatility of the dimer product; ^(c)Comparative catalysts andpolymerization examples.

Metallocene compounds used in the polymerization processes of Examples1-36, have structures as follows:

1A

B

C

D

E

F (comparative)

G (comparative)

H (comparative)

J

K (comparative)

L

1-Decene Polymerizations using N,N-dimethylaniliniumtetrakisperfluoronaphthylborate Activator

TABLE II below shows Examples 37-42, using N,N-dimethylaniliniumtetrakisperfluoronaphthylborate as an activator, listing reactionconditions including identity of the metallocene compound (MC), thepolymerization temperature, the yield of isolated PAO, the catalystactivity, together with Mn, as measured by ¹H NMR, and the distributionsof the olefins in terms of mole percentages of each type, on the basisof the total moles of the four categories of olefins.

TABLE II Catalyst 0.08 μmol (0.4 mmol/l in toluene), with 0.08 μmolN,N-Dimethylanilinium tetrakisperfluoronaphthylborate activator (0.4mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l in isohexane), 2mL 1-Decene, isohexane solvent, 1 h. Conditions Temp Activity OlefinsDistribution (%) Yield Mn* Conv. Ex. # MC (° C.) (g/s · mol) Di Vi TriVd (g) (g/mol) %** 37 a 1A 60 696 1.2 7.3 8.8 82.7 0.200 1885 13.5 b 60663 1.1 7.2 8.6 83.2 0.191 2009 12.9 38 a 1A 85 1350 0.9 7.6 7.6 83.80.388 772 26.2 b 85 1280 0.6 7.4 7.4 84.6 0.369 796 24.9 39 a 1A 1102050 0.4 5.5 6.6 87.5 0.590 456 39.8 b 110 2340 0.4 5.2 6.7 87.7 0.674460 45.5 40 a D 60 2600 1.0 34.7 8.7 55.6 0.750 4353 50.6 b 60 2500 1.733.2 10.3 54.8 0.719 4353 48.5 41 a D 85 3280 1.0 31.9 6.4 60.7 0.9461405 63.8 b 85 3480 0.9 30.8 7.4 60.9 1.00 1349 67.5 42 a D 110 3850 1.019.3 5.8 73.9 1.11 657 74.9 b 110 3690 0.7 21.8 6.6 71.0 1.06 669 71.5*Mn estimated by ¹H NMR. **Conv. % calculated from isolated yield and itis the minimum conversion due to volatility of the dimer product.

1-Decene Polymerizations using N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate Activator

TABLE 3 below compares metallocene catalysts 1A, 2, 3, and 4, and TABLE4 compares metallocene catalysts 5 through 17 listing reactionconditions including identity of the metallocene compound (MC), thepolymerization temperature, the isolated yield of PAO, together with Mn,as measured by ¹H NMR, and the distributions of the olefins in terms ofmole percentages of each type, on the basis of the total moles of thefour categories of olefins. Conversion (%)=(grams isolated PAO/gramsalpha-olefin used)×100.

Samples of each catalyst system were repeated at three polymerizationtemperatures (60° C., 85° C., and 110° C.), with each sample being testtwice at each temperature. Data in the tables show that polymerizationusing certain inventive metallocene compounds resulted inextraordinarily high selectivity toward vinylidenes or toward acombination of vinylidenes and tri-substituted vinylenes, and ingeneral, a very low selectivity toward di-substituted vinylenes andtoward vinyl groups. As such, the uPAO product mixtures from thoseinventive metallocene compounds may be particularly useful asintermediates for making hydrogenated and/or functionalized PAOmaterials, where the reactivity of vinylidenes and/or tri-substitutedvinylenes are particularly high (and therefore desired).

Metallocene Catalysts

TABLE 3 Catalyst 0.08 μmol (0.4 mmol/l in toluene), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (BF20) activator(0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Iso-lated % % Mn* TYield % Tri- % % Mn* Vinylidene (avg) Conv EX (° C.) MC (g) Vinylene subVinyl Vinylidene g/mol (avg) (g/mol) %** 43A 60  1A 0.3942 0.7 2.6 3.693.1 1166 93.5 1153 26.6 43B 60  1A 0.4087 0.5 2.3 3.4 93.8 1140 27.644A 85  1A 0.6694 0.3 2.6 3.3 93.7 555 93.8 537 45.2 44B 85  1A 0.58940.4 2.7 3.1 93.8 520 39.8 45A 110  1A 0.8086 0.2 2.9 1.0 95.9 371 95.9372 54.6 45B 110  1A 0.8092 0.2 2.8 1.2 95.8 372 54.6 46A 60 2 0.10970.4 1.1 0.8 97.8 504 97.9 519 7.4 46B 60 2 0.1064 0.4 1.0 0.7 97.9 5337.2 47A 85 2 0.194 0.1 0.8 0.1 99.0 324 99.0 325 13.1 47B 85 2 0.17620.1 0.8 0.2 98.9 327 11.9 48A 110 2 0.3025 0.2 1.3 0.2 98.3 303 98.5 30320.4 48B 110 2 0.2614 0.1 1.1 0.1 98.7 303 17.6 49A 60 3 0.1548 0.3 0.70.9 98.1 622 97.7 620 10.4 49B 60 3 0.1594 0.4 1.1 1.3 97.2 618 10.8 50A85 3 0.4458 0.8 2.1 1.2 95.9 367 97.0 373 30.1 50B 85 3 0.4442 0.2 0.90.7 98.2 379 30.0 51A 110 3 0.8584 0.1 1.3 0.2 98.4 320 98.1 317 57.951B 110 3 0.8568 0.3 1.6 0.4 97.7 315 57.8 52A 60 4 0.1827 0.3 3.1 4.791.9 1313 91.9 1298 12.3 52B 60 4 0.1844 0.3 3.2 4.6 91.9 1284 12.4 53A85 4 0.7312 0.1 3.5 6.7 89.8 722 89.5 710 49.3 53B 85 4 0.5846 0.2 4.06.6 89.2 699 39.4 54A 110 4 0.8993 0.3 4.7 5.8 89.2 426 89.8 430 60.754B 110 4 0.9406 0.2 4.0 5.4 90.4 435 63.5 *Mn estimated by ¹H NMR,**Conv % calculated from isolated yield and it is the minimum conversiondue to volatility of the dimer product.

Catalysts numbered 5 through 17 were prepared as described above.Polymerization conditions utilized 0.08 μmol of the indicated catalystwith the N,N-Dimethylanilinium Tetrakisperfluorophenylborate activator,2 mL 1-decene, isohexane solvent and a 1 h reaction time at theindicated temperature. These data are shown in Table 4.

TABLE 4 Catalyst 0.08 μmol (0.4 mmol/l in toluene), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (BF20) activator(0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Isolated % % Mn* TYield % Tri- % % Mn* Vinylidene (avg) Conv EX (° C.) MC (g) Vinylene subVinyl Vinylidene g/mol (avg) (g/mol) %** 55A 60 5 1.2132 1.5 5.7 2.490.4 2552 90.4 2592  81.9 55B 60 5 1.1997 1.5 5.7 2.4 90.4 2632 81.0 56A85 5 1.2801 1.2 8.9 1.2 88.8 914 88.7 917 86.4 56B 85 5 1.2557 1.2 9.11.1 88.6 921 84.7 57A 110 5 1.1828 1.1 11.4 1.0 86.5 534 86.1 536 79.857B 110 5 1.2055 1.2 12.1 1.0 85.7 538 81.3 58A 60 6 0.0278 0.6 0.6 0.398.5 552 98.1 551 1.9 58B 60 6 0.0285 0.6 1.1 0.6 97.6 549 1.9 59A 85 60.1436 0.4 1.0 0.4 98.2 356 98.1 353 9.7 59B 85 6 0.1477 0.4 1.1 0.498.1 351 10.0 60A 110 6 0.3657 0.5 1.5 0.3 97.8 314 98.1 314 24.7 60B110 6 0.3488 0.2 1.1 0.2 98.4 315 23.5 61A 60 7 0.1337 0.6 4.0 7.2 88.21919 87.2 1913  9.0 61B 60 7 0.1306 0.6 5.2 7.8 86.3 1907 8.8 62A 85 70.1532 0.5 5.4 9.3 84.8 872 85.4 874 10.3 62B 85 7 0.1626 0.5 4.6 8.986.0 876 11.0 63A 110 7 0.1944 0.4 4.9 8.8 85.9 507 86.2 520 13.1 63B110 7 0.2602 0.3 4.7 8.5 86.4 532 17.6 64A 60 8 0.1246 0.5 1.2 1.0 97.3583 96.6 588 8.4 64B 60 8 0.1245 0.5 1.9 1.8 96.0 593 8.4 65A 85 80.4319 0.2 1.2 0.8 97.8 369 97.8 368 29.1 65B 85 8 0.4452 0.2 1.2 0.797.9 367 30.0 66A 110 8 0.8973 0.0 1.1 0.2 98.6 317 98.4 317 60.5 66B110 8 0.9322 0.1 1.4 0.3 98.2 317 62.9 67A 60 9 0.0323 0.0 3.3 1.3 95.4507 95.3 513 2.2 67B 60 9 0.0326 0.0 3.3 1.6 95.1 518 2.2 68A 85 90.1665 0.0 3.2 0.7 96.1 330 96.4 327 11.2 68B 85 9 0.1832 0.0 3.0 0.496.6 325 12.4 69A 110 9 0.1824 0.0 2.3 0.3 97.4 309 97.3 307 12.3 69B110 9 0.226 0.0 2.5 0.4 97.1 306 15.2 70A 60 10 0.0695 0.5 1.3 1.3 96.8794 97.5 794 4.7 70B 60 10 0.0622 0.4 1.2 0.1 98.2 794 4.2 71A 85 100.0821 0.3 1.3 2.0 96.4 490 96.7 489 5.5 71B 85 10 0.0913 0.3 1.1 1.797.0 488 6.2 72A 110 10 0.1419 0.1 1.2 1.2 97.4 362 97.3 361 9.6 72B 11010 0.1801 0.2 1.3 1.3 97.2 360 12.2 73A 60 11 0.0917 0.3 0.8 1.0 97.9636 97.3 630 6.2 73B 60 11 0.092 0.4 1.4 1.5 96.7 625 6.2 74A 85 110.2414 0.1 0.9 1.1 98.0 406 98.0 399 16.3 74B 85 11 0.2651 0.1 0.9 1.098.0 393 17.9 75A 110 11 0.6764 0.0 1.2 0.5 98.3 317 98.3 317 45.6 75B110 11 0.6827 0.0 1.1 0.5 98.4 317 46.1 76A 60 12 0.039 — — — — — — —2.6 76B 60 12 0.0351 — — — — — 2.4 77A 85 12 0.1596 0.3 1.5 0.2 98.0 34497.8 345 10.8 77B 85 12 0.1621 0.3 1.7 0.4 97.6 346 10.9 78A 110 120.2002 0.8 2.7 0.0 96.4 311 97.2 313 13.5 78B 110 12 0.2236 0.3 1.7 0.098.0 315 15.1 79A 60 13 0.5464 3.4 5.3 2.3 89.0 1191 91.0 1246  36.9 79B60 13 0.5493 2.6 3.4 1.0 93.0 1301 37.1 80A 85 13 0.8176 1.6 4.5 0.693.4 550 93.3 553 55.2 80B 85 13 0.8451 1.6 4.6 0.6 93.2 557 57.0 81A110 13 0.9876 1.3 6.8 0.1 91.8 382 91.9 383 66.6 81B 110 13 0.9961 1.26.7 0.1 91.9 385 67.2 82A 60 14 0.0467 — — — — — — — 3.2 82B 60 140.0462 — — — — — 3.1 83A 85 14 0.1268 4.0 3.7 1.8 90.5 854 90.4 847 8.683B 85 14 0.1369 3.9 3.8 1.9 90.3 839 9.2 84A 110 14 0.0899 2.0 5.1 2.690.4 593 90.6 585 6.1 84B 110 14 0.0912 1.6 5.0 2.4 90.9 577 6.2 85A 6015 0.0207 — — — — — — — 1.4 85B 60 15 0.0209 — — — — — 1.4 86A 85 150.0974 0.3 1.4 0.9 97.4 365 97.6 361 6.6 86B 85 15 0.1094 0.4 1.3 0.697.7 358 7.4 87A 110 15 0.2949 1.2 2.7 0.7 96.0 298 97.2 305 19.9 87B110 15 0.3415 0.3 1.2 0.1 98.4 312 23.0 88A 60 16 0.1052 0.5 4.2 6.888.6 1780 89.3 1770  7.1 88B 60 16 0.1152 0.4 3.3 6.2 90.1 1760 7.8 89A85 16 0.1241 0.6 4.9 8.9 85.6 857 83.9 815 8.4 89B 85 16 0.1415 1.4 7.78.8 82.2 773 9.5 90A 110 16 0.1986 0.3 5.5 10.4  83.8 661 85.3 586 13.490B 110 16 0.2248 0.4 4.6 8.2 86.8 511 15.2 91A 60 17 0.0195 — — — — — —— 1.3 91B 60 17 0.0189 — — — — — 1.3 92A 85 17 0.0735 — — — — — — — 5.092B 85 17 0.0929 — — — — — 6.3 93A 110 17 0.2384 0.2 1.3 0.4 98.1 31497.1 310 16.1 93B 110 17 0.2354 0.9 2.4 0.6 96.1 305 15.9 *Mn estimatedby ¹H NMR; **Conv % calculated from isolated yield and it is the minimumconversion due to volatility of the dimer product. “—” indicatesinsufficient material for analysis or data not available.

1-Decene Polymerizations using N,N-dimethylaniliniumtetrakisperfluoronaphthylborate Activator

TABLE 5 Catalyst 0.04 μmol (0.8 mmol/l in toluene), with 0.04 μmolN,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate as activator(0.8 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-decene, isohexane solvent. 1 h. Isolated % % Mn* TYield % Tri- % % Mn* Vinylidene (avg) Conv EX (° C.) MC (g) Vinylene subVinyl Vinylidene g/mol (avg) (g/mol) %** 94A 85 18 0.0594 0.5% 6.3 5.188.2 521 87.6 533 4.0 94B 85 18 0.0539 0.6% 7.2 5.2 87.0 546 3.6 95A 8519 0.1231 0.7% 4.3 3.8 91.3 492 91.5 496 8.3 95B 85 19 0.1287 0.6% 4.23.5 91.7 501 8.7 *Mn estimated by ¹H NMR. **Conv % calculated fromisolated yield and it is the minimum conversion due to volatility of thedimer product.

As shown in Tables 3 and 4, and further illustrated in FIGS. 1 and 2,inventive catalysts 2, 3, 6, 8, 9, 10, 11, 12, 14, 15, and 17 have evenhigher vinylidene selectivity of greater than or equal to 96% thancatalyst 1A, which produced PAOs having 93-95.9% vinylidene, across alltemperatures tested. Notably, catalysts 2 and 3 also show capabilitiesfor much desired lower M_(n) in comparison to catalyst 1A, all undersimilar polymerization conditions using similar drying/isolationprocedures. As these data also show, catalyst 4, which is used in otherpolymerization processes, a 1-Me-indenyl metallocene, was furtherdiscovered to be useful for producing low viscosity, low Mn unsaturatedPAOs, showing vinylidene terminations of 89-92 mol % under similarconditions. The Zr version of 4, catalyst 12, gives high vinylideneselectivities but has much lower activities in comparison to catalyst 3.

It is considered that even small changes in metallocene compoundstructure can cause drastic differences in the characteristics of theoligomeric products. For instance, the only difference betweenmetallocene D and metallocene A is a single methyl group, instead of ahydrogen, at the R³ position (alpha to the naphthyl portion of thebenzindenyl ring and beta to the R¹ methyl group on the cyclopentadienylportion of the benzindenyl ring). Despite that relatively smallstructural difference, as shown in Table I (Ex. 13-14 vs. Ex. 1-2),using same activator (dimethylanilinium tetrakisperfluorophenylborate)and under same conditions, a catalyst system comprising metallocene Dcan be seen to produce a uPAO product having a significant vinylcontent, whereas a catalyst system comprising metallocene A can be seento produce a uPAO product having an extraordinarily high vinylidenecontent (and very little vinyl content). A similar trend has beenobserved using dimethylanilinium tetrakisperfluoronaphthylborate as anactivator (Table II, Ex. 40-42 vs. Ex. 37-39). These results show boththe unexpectedness of the uPAO product characteristics and theunpredictability of the effect of ligand structure change on metallocenecatalysis.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related applications, and/or testing proceduresto the extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is not incorporated by reference herein. As shouldbe apparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Individual elements or features of aparticular embodiment are generally not limited to that particularembodiment, but, where applicable, are interchangeable and can be usedin a selected embodiment, even if not specifically shown or described.The same may also be varied in many ways. Such variations are not to beregarded as a departure from the invention, and all such modificationsare intended to be included within the scope of the invention.Accordingly, it is not intended that the invention be limited thereby.Likewise, the term “comprising” is considered synonymous with the terms“including” and “containing.” Also, whenever a composition, an element,or a group of elements is preceded with the transitional phrase“comprising,” it should be understood that the same composition or groupof elements is contemplated with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements, and vice versa.

1-25. (canceled)
 26. An unsaturated poly alpha-olefin (PAO) productcomprising greater than or equal to about 80 mol % vinylidenes, based ontotal moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes contained therein and having an Mn of lessthan 5000 g/mol as determined by ¹H NMR.
 27. The unsaturated polyalpha-olefin (PAO) product of claim 26 further comprising: 96.5 mol % to99.9 mol % of vinylidenes; 0.1 mol % to 3.5 mol % of tri-substitutedvinylenes; 3.0 mol % or less of di-substituted vinylenes; 3.0 mol % orless of vinyl groups; based on total moles of vinylidenes,tri-substituted vinylenes, di-substituted vinylenes, and vinylidenescontained therein; and a number average molecular weight (Mn) of 1500g/mol or less as measured by ¹H NMR.
 28. The unsaturated polyalpha-olefin (PAO) product of claim 26 further comprising less than orequal to about 1.0 mol % di-substituted vinylenes, when present; lessthan or equal to about 1.0 mol % vinyl groups when present; and a numberaverage molecular weight (Mn) of 1000 g/mol or less as measured by ¹HNMR.
 29. The unsaturated poly alpha-olefin (PAO) product of claim 26further comprising greater than or equal to about 80 mol % vinylidenes,based on total moles of vinyls, vinylidenes, di-substituted vinylenes,and tri-substituted vinylenes contained therein, and from 98 mol % to99.5 mol % of a combination of vinylidenes and tri-substitutedvinylenes; 0.5 mol % to 2 mol % of a combination of di-substitutedvinylenes and vinyl groups; and a number average molecular weight (Mn)of 800 g/mol or less as measured by ¹HNMR.
 30. A catalyst compoundsuitable to produce an unsaturated PAO product from C₆-C₃₂ alpha-olefinunder polymerization conditions, comprising: a polymerizationselectivity suitable to form an unsaturated PAO product comprising:greater than or equal to about 80 mol % vinylidenes, based on totalmoles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; represented bythe formula (F-MC2):

in which one of R¹, R², and R³ is an alpha Group 14 atom directlyattached to the indenyl ring, and a beta Group 14 atom attached to thealpha atom, and two or more substituted or unsubstituted linear,branched linear, or cyclic C₁-C₈ hydrocarbyl groups attached to the betaatom, and two of R¹, R², and R³ are each hydrogen; R⁶, R⁷, R⁸, R⁹, R¹⁰,and R¹¹ are each independently a hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup; R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl group; R¹⁶ is a hydrogen, a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl group orsilylcarbyl group; each X is independently a halogen, a hydride, anamide, an alkoxide, a sulfide, a phosphide, a diene, an amine, aphosphine, an ether, or a C₁-C₂₀ substituted or unsubstituted linear,branched linear, or cyclic hydrocarbyl group, or two or more X moietiestogether form a fused ring or ring system; M is a group 3, 4 or 5transition metal having an integer coordination number of v; and m is aninteger equal to v-2.
 31. The catalyst compound of claim 30, wherein thepolymerization selectivity is suitable to form an unsaturated PAOproduct comprising: 96.5 mol % to 99.9 mol % of vinylidenes; 0.1 mol %to 3.5 mol % of tri-substituted vinylenes; 2.0 mol % or less ofdi-substituted vinylenes; 2.0 mol % or less of vinyl groups; based ontotal moles of vinyls, vinylidenes, di-substituted vinylenes, andtri-substituted vinylenes in the unsaturated PAO product; and a numberaverage molecular weight (Mn) of 1500 g/mol or less as measured by ¹HNMR.
 32. A catalyst compound represented by formula (I):

wherein: a first one of R¹ or R³ is a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl group; a secondone of R¹, R², and R³ is a hydrogen; the third one of R¹, R², and R³ isa hydrogen; R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, asubstituted or unsubstituted linear, branched, or cyclic C₁-C₃₀hydrocarbyl group, or two of R⁶, R⁷, R¹⁷, and R¹⁸ taken together withthe carbon atoms in the indenyl ring to which they are directlyconnected, collectively form one or more substituted or unsubstitutedrings annelated to the indenyl ring; and R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ areeach independently a substituted or unsubstituted linear, branched, orcyclic C₁-C₂₀ hydrocarbyl group or R¹⁶ may be a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ silylcarbyl group; oreach X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched, or cyclic hydrocarbylgroup, or two or more X moieties together form a fused ring or ringsystem; M is a group 3, 4 or 5 transition metal having an integercoordination number of v; and m is an integer equal to v-2.
 33. Thecatalyst compound of claim 32 wherein the compound is represented byformula (II):

wherein: R¹ and R² are hydrogen; Q is a substituted hydrocarbyl thatcomprises one or more Group 14 atoms; R¹⁹ is C; R²⁰, R²¹, and R²² areindependently hydrogen or a substituted or unsubstituted linear,branched, or cyclic C₁-C₂₀ hydrocarbyl group, wherein at least two ofR²⁰, R²¹, and R²² are a substituted or unsubstituted linear, branched,or cyclic C₁-C₂₀ hydrocarbyl group; R⁶, R⁷, R¹⁷, and R¹⁸ are eachindependently hydrogen, a substituted or unsubstituted linear, branched,or cyclic C₁-C₃₀ hydrocarbyl group, or two of R⁶, R⁷, R¹⁷, and R¹⁸ takentogether with the carbon atoms in the indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings annelated to the indenyl ring; and R¹², R¹³, R¹⁴,R¹⁵, and R¹⁶ are each independently a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₂₀ hydrocarbyl group; or each X isindependently a halogen, a hydride, an amide, an alkoxide, a sulfide, aphosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched, or cyclic hydrocarbylgroup, or two or more X moieties together form a fused ring or ringsystem; M is a group 3, 4 or 5 transition metal having an integercoordination number of v; and m is an integer equal to v-2.
 34. Thecatalyst compound of claim 32 wherein the compound is represented byformula:

wherein: R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently hydrogen, asubstituted or unsubstituted linear, branched, or cyclic C₁-C₃₀hydrocarbyl group, or two of R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ taken togetherwith the carbon atoms in the benz-indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings annelated to the benz-indenyl ring; and R¹², R¹³,R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₂₀ hydrocarbyl group; each X isindependently a halogen, a hydride, an amide, an alkoxide, a sulfide, aphosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched, or cyclic hydrocarbylgroup, or two or more X moieties together form a fused ring or ringsystem; M is a group 3, 4 or 5 transition metal having an integercoordination number of v; and m is an integer equal to v-2.
 35. Thecatalyst compound of claim 32 wherein the compound is represented byformula:

wherein: R⁶, R¹⁸, R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷ are each independentlyhydrogen, a substituted or unsubstituted linear, branched, or cyclicC₁-C₃₀ hydrocarbyl group, or two of R⁶, R¹⁸, R²⁹, R²⁴, R²⁵, R²⁶, and R²⁷taken together with the carbon atoms in the cyclopentan-indenyl ring towhich they are directly connected, collectively form one or moresubstituted or unsubstituted rings annelated to the cyclopentan-indenylring; and R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently asubstituted or unsubstituted linear, branched, or cyclic C₁-C₂₀hydrocarbyl group; each X is independently a halogen, a hydride, anamide, an alkoxide, a sulfide, a phosphide, a diene, an amine, aphosphine, an ether, a C₁-C₂₀ substituted or unsubstituted linear,branched, or cyclic hydrocarbyl group, or two or more X moietiestogether form a fused ring or ring system; M is a group 3, 4 or 5transition metal having an integer coordination number of v; and m is aninteger equal to v-2.
 36. The catalyst compound according to claim 31,comprising a polymerization selectivity suitable to form an unsaturatedPAO product comprising: greater than or equal to about 96.5 mol %vinylidenes; less than or equal to about 3.5 mol % tri-substitutedvinylenes; less than or equal to about 1.0 mol % di-substitutedvinylenes, when present; less than or equal to about 1.0 mol % vinylgroups when present; based on total moles of vinyls, vinylidenes,di-substituted vinylenes, and tri-substituted vinylenes in theunsaturated PAO product; and a number average molecular weight (Mn) of1500 g/mol or less as measured by ¹H NMR.
 37. A catalyst compoundrepresented by formula (III-B), (IV-B), (VI), (VIII), (IX), (X), (XI),(XII), (XV), (XVII), (XVIII), or (XIX):

wherein each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched, orcyclic hydrocarbyl group, or two or more X moieties may together form afused ring or ring system; M is a group 3, 4 or 5 transition metalhaving an integer coordination number of v; and m is an integer equal tov-2.
 38. The catalyst compound of claim 33, wherein Q is carbon and R¹⁹is carbon or silicon. 39-45. (canceled)
 46. The unsaturated polyalpha-olefin product of claim 26 wherein the unsaturated polyalpha-olefin product is represented by the following formula (F-1):

where R¹, R^(2a), R^(2b), R³, each of R⁴ and R⁵, R⁶, and R⁷, the same ordifferent at each occurrence, independently represents a hydrogen or asubstituted or unsubstituted hydrocarbyl, and n is a non-negativeinteger corresponding to the degree of polymerization, where R¹ is nothydrogen, and both R^(2a) and R^(2b) are hydrogen and n is
 0. 47. Theunsaturated poly alpha-olefin product of claim 27 wherein theunsaturated poly alpha-olefin product is represented by the followingformula (F-1):

where R¹, R^(2a), R^(2b), R³, each of R⁴ and R⁵, R⁶, and R⁷, the same ordifferent at each occurrence, independently represents a hydrogen or asubstituted or unsubstituted hydrocarbyl, and n is a non-negativeinteger corresponding to the degree of polymerization, where R¹ is nothydrogen, and both R^(2a) and R^(2b) are hydrogen and n is
 0. 48. Theunsaturated poly alpha-olefin product of claim 28 wherein theunsaturated poly alpha-olefin product is dimer.
 49. The unsaturated polyalpha-olefin product of claim 29 wherein the unsaturated polyalpha-olefin product is dimer. 50-65. (canceled)
 66. The compound ofclaim 33, wherein Q comprises C.
 67. The compound of claim 33, whereinR⁷ and R¹⁷ taken together with the carbon atoms in the indenyl ring towhich they are directly connected, collectively form one or moresubstituted or unsubstituted rings annelated to the indenyl ring. 68.The catalyst compound of claim 32 wherein the compound is represented byformula (II):

wherein: R¹ and R² are hydrogen; Q comprises Group 14 atoms; R¹⁹ is Si;R²⁰, R²¹, and R²² are independently hydrogen or a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group,wherein at least two of R²⁰, R²¹, and R²² are a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group; R⁶,R⁷, R¹⁷, and R¹⁸ are each independently hydrogen, a substituted orunsubstituted linear, branched, or cyclic C₁-C₃₀ hydrocarbyl group, andR⁷ and R¹⁷ taken together with the carbon atoms in the indenyl ring towhich they are directly connected, collectively form one or moresubstituted or unsubstituted rings annelated to the indenyl ring; andR¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group; oreach X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched, or cyclic hydrocarbylgroup, or two or more X moieties together form a fused ring or ringsystem; M is a group 3, 4 or 5 transition metal having an integercoordination number of v; and m is an integer equal to v-2.
 69. Thecatalyst compound of claim 33, wherein Q comprises C; R²¹ is H; and R²⁰and R²² are C₁ hydrocarbyl group.
 70. The unsaturated poly alpha-olefin(PAO) product of claim 26 wherein the PAO product comprises greater thanor equal to about 90 mol % vinylidenes, based on total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenescontained therein and having an Mn of less than 5000 g/mol as determinedby ¹H NMR.
 71. A process for making a poly alpha-olefin, PAO, theprocess comprising: contacting a feed comprising a C₆-C₃₂ alpha-olefinwith a catalyst system comprising a metallocene compound in apolymerization reactor under polymerization conditions to effect apolymerization reaction to obtain a polymerization reaction mixturecomprising vinylidenes, tri-substituted vinylenes, optionallydi-substituted vinylenes, and optionally vinyls; and obtaining anunsaturated PAO product from the polymerization reaction mixture,wherein the unsaturated PAO product comprises vinylidenes,tri-substituted vinylenes, optionally di-substituted vinylenes,optionally vinyls, wherein the conversion is about 10% or more and thepolymerization reaction exhibits a selectivity toward greater than orequal to about 80 mol % vinylidenes, based on total moles of vinyls,vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes inthe unsaturated PAO product, wherein the metallocene compound isrepresented by formula (F-MC):

wherein: R² is hydrogen and one of R¹ and R³ is a substituted orunsubstituted linear, branched, or cyclic C₁-C₆ hydrocarbyl group, andthe other one of R¹ and R³ is a hydrogen; R⁴ and R⁵ taken together withthe carbon atoms in the cyclopentadienyl ring to which they are directlyconnected, collectively form one or more substituted or unsubstitutedrings annulated to the cyclopentadienyl ring; R¹², R¹³, R¹⁴, R¹⁵, andR¹⁶ are each independently a hydrogen, or a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₂₀ hydrocarbyl, silylcarbyl, or germanylgroup, and optionally at least three of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ arenot hydrogen; M is a group 3, 4 or 5 transition metal having an integercoordination number of v; wherein v is 3, 4, or 5, each X isindependently a halogen, a hydride, an amide, an alkoxide, or a C₁-C₂₀substituted or unsubstituted linear, branched, or cyclic hydrocarbylgroup, or optionally two or more X moieties together form a fused ringor ring system; and m is an integer equal to v-2.
 72. The process ofclaim 71, wherein: one of substituted hydrocarbyls R¹ and R³ comprise analpha Group 14 atom directly attached to the indenyl ring, a beta Group14 atom attached to the alpha atom, and two or more, substituted orunsubstituted linear, branched linear, or cyclic C₁-C₈ hydrocarbylgroups attached to the beta atom.
 73. The process of claim 71, whereinthe metallocene compound is represented by formula (II):

wherein: R¹ and R² are hydrogen; R³ comprises R²³ and R¹⁹ which compriseone or more Group 14 atoms; R²⁰, R²¹, and R²² are independently hydrogenor a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀hydrocarbyl group and at least two of R²⁰, R²¹, and R²² areindependently a substituted or unsubstituted linear, branched, or cyclicC₁-C₂₀ hydrocarbyl group, wherein at least two of R²⁰, R²¹, and R²² area substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀hydrocarbyl group; R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen;a substituted or unsubstituted linear, branched, or cyclic C₁-C₃₀hydrocarbyl group; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, takentogether with the carbon atoms in the indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings annulated to the indenyl ring; R¹², R¹³, R¹⁴, R¹⁵,and R¹⁶ are each independently a substituted or unsubstituted linear,branched, or cyclic C₁-C₈ hydrocarbyl group; each X is independently ahalogen, a hydride, an amide, an alkoxide, or a C₁-C₂₀ substituted orunsubstituted linear, branched, or cyclic hydrocarbyl group, or two ormore X moieties together form a fused ring or ring system; M is a group3, 4 or 5 transition metal having an integer coordination number of v;wherein v is 3, 4, or 5, and m is an integer equal to v-2.
 74. Theprocess of claim 72, wherein: one of substituted hydrocarbyls R¹ and R³comprise an alpha Group 14 atom directly attached to the indenyl ring, abeta Group 14 atom attached to the alpha atom, and two or more,substituted or unsubstituted linear, branched linear, or cyclic C₁-C₈hydrocarbyl groups attached to the beta atom.
 75. The process of claim73, wherein R²³ and R¹⁹ comprise one or more silicon atoms.